N-cycloalkyl-n-[(cycloalkenylphenyl)methylene]-(thio)carboxamide derivatives

ABSTRACT

The present invention relates to fungicidal N-cycloalkyl-N-[(cycloalkenylphenyl)methylene]carboxamide derivatives and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

The present invention relates to fungicidalN-cycloalkyl-N-[(cycloalkenylphenyl)methylene]carboxamide derivativesand their thiocarbonyl derivatives, their process of preparation andintermediate compounds for their preparation, their use as fungicides,particularly in the form of fungicidal compositions and methods for thecontrol of phytopathogenic fungi of plants using these compounds ortheir compositions.

In international patent application WO-2007/087906 certainN-cycloalkyl-N-benzyl-carboxamides are generically embraced in a broaddisclosure of numerous compounds of the following formula:

wherein A represents a carbo-linked, partially saturated or unsaturated,5-membered heterocyclyl group, Z¹ represents a substituted or nonsubstituted C₃-C₇-cycloalkyl group, n is equal to 1 to 5 and X canrepresent various substituents among which a C₂-C₈-alkenyl orC₂-C₈-halogenoalkenyl group. However, there is no explicit disclosure orsuggestion to select in this document of any such derivative wherein Xcan represent a substituted or non-substituted cycloalkenyl group.

In international patent application WO-2009/016220 certainN-cycloalkyl-N-benzyl-thiocarboxamides are generically embraced in abroad disclosure of numerous compounds of the following formula:

wherein A represents a carbo-linked, partially saturated or unsaturated,5-membered heterocyclyl group, T can represent S, Z¹ represents asubstituted or non substituted C₃-C₇-cycloalkyl group, n is equal to 1to 5 and X can represent various substituents among which aC₂-C₈-alkenyl or C₂-C₈-halogenoalkenyl group. However, there is noexplicit disclosure or suggestion to select in this document of any suchderivative wherein X can represent a substituted or non-substitutedcycloalkenyl group.

In international patent application WO-2010/130767 certainN-cycloalkyl-N-benzyl-carboxamides or thiocarboxamides are genericallyembraced in a broad disclosure of numerous compounds of the followingformula:

wherein X¹ and X² represent a fluorine of a chlorine atom, T canrepresent O or S, Z¹ represents a substituted or non substitutedC₃-C₇-cycloalkyl group, Y can represent CR⁵ and R¹, R², R³, R⁴ or R⁵can, independently, represent various substituents among which asubstituted or non substituted C₂-C₈-alkenyl group or aC₂-C₈-halogenoalkenyl group. However, there is no explicit disclosure orsuggestion to select in this document of any such derivative wherein R¹or R² or R³ or R⁴ or R⁵ can represent a substituted or non-substitutedcycloalkenyl group.

In international patent application WO-2009/024342 certainN-(cycloalkenylphenyl)methylene-carboxamides are generically embraced ina broad disclosure of numerous compounds of the following formula:

wherein R₁ represents a C₁-C₄-alkyl group, R₂ represents aC₁-C₄-haloalkyl group, B can represent a phenyl group that can besubstituted by various substituents among which a substituted or nonsubstituted C₂-C₆-alkenyl group and R₁₅ can represent hydrogen or aC₃-C₇-cycloalkyl group with the proviso that B is different from phenylif R₁₅ represents a C₃-C₇-cycloalkyl group. Therefore, there is nodisclosure in this document of any such derivative wherein R₁₅ canrepresent a C₃-C₇-cycloalkyl group and B be simultaneously a substitutedphenyl group.

Accordingly, the present invention provides aN-cycloalkyl-N-[(cycloalkenylphenyl)methylene](thio) carboxamide offormula (I)

wherein

-   -   A represents a carbo-linked, unsaturated or partially saturated,        5-membered heterocyclyl group that can be substituted by up to        four groups R that can be the same or different;    -   T represents O or S;    -   n represents 0, 1, 2, 3 or 4;    -   m represents 0, 1, 2, 3, 4 or 5;    -   p represents 1, 2, 3 or 4;    -   Z¹ represents a non-substituted C₃-C₇-cycloalkyl or a        C₃-C₇-cycloalkyl substituted by up to 10 atoms or groups that        can be the same or different and that can be selected in the        list consisting of halogen atoms, cyano, C₁-C₈-alkyl,        C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be        the same or different, C₁-C₈-alkoxy, C₁-C₈-halogenoalkoxy        comprising up to 9 halogen atoms that can be the same or        different, C₁-C₈-alkoxycarbonyl, C₁-C₈-halogenoalkoxycarbonyl        comprising up to 9 halogen atoms that can be the same or        different, C₁-C₈-alkylaminocarbonyl and        di-C₁-C₈-alkylaminocarbonyl;    -   Z² and Z³, which can be the same or different, represent a        hydrogen atom; substituted or non substituted C₁-C₈-alkyl;        substituted or non substituted C₂-C₈-alkenyl; substituted or non        substituted C₂-C₈-alkynyl; cyano; isonitrile; nitro; a halogen        atom; substituted or non substituted C₁-C₈-alkoxy; substituted        or non substituted C₂-C₈-alkenyloxy; substituted or non        substituted C₂-C₈-alkynyloxy; substituted or non substituted        C₃-C₇-cycloalkyl; substituted or non substituted        C₁-C₈-alkylsulfanyl; substituted or non substituted        C₁-C₈-alkylsulfonyl; substituted or non substituted        C₁-C₈-alkylsulfinyl; amino; substituted or non substituted        C₁-C₈-alkylamino; substituted or non substituted        di-C₁-C₈-alkylamino; substituted or non substituted        C₁-C₈-alkoxycarbonyl; substituted or non substituted        C₁-C₈-alkylcarbamoyl; substituted or non substituted        di-C₁-C₈-alkylcarbamoyl; or substituted or non substituted        N—C₁-C₈-alkyl-C₁-C₈-alkoxy-carbamoyl; or    -   Z² and Z³ together with the carbon atom to which they are linked        can form a substituted or non substituted C₃-C₇ cycloalkyl; or    -   Z³ and the substituent X vicinal to the point of attachment of        the phenyl ring, together with the consecutive carbon atoms to        which they are linked, can form a substituted or non substituted        5-, 6- or 7-membered, partly saturated, carbo- or hetero-cycle        comprising up to 3 heteroatoms and Z² is herein-described;    -   X independently represents a halogen atom; nitro; cyano;        isonitrile; hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl;        formyl; formyloxy; formylamino; substituted or non-substituted        (hydroxyimino)-C₁-C₈-alkyl; substituted or non-substituted        (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or non-substituted        (C₂-C₈-alkenyloxyimino)-C₁-C₈-alkyl; substituted or        non-substituted (C₂-C₈-alkynyloxyimino)-C₁-C₈-alkyl; substituted        or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; carboxy;        carbamoyl; N-hydroxycarbamoyl; carbamate; substituted or        non-substituted C₁-C₃-alkyl; C₁-C₈-halogenoalkyl having 1 to 9        halogen atoms; substituted or non-substituted C₂-C₈-alkenyl;        C₂-C₈-halogenoalkenyl having 1 to 9 halogen atoms; substituted        or non-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1        to 9 halogen atoms; substituted or non-substituted C₁-C₈-alkoxy;        C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms; substituted or        non-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl        having 1 to 9 halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 9        halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 9        halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;        substituted or non-substituted di-C₁-C₈-alkylamino; substituted        or non-substituted C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy        having 1 to 9 halogen atoms; substituted or non-substituted        C₃-C₈-alkynyloxy; C₂-C₈-halogenoalkynyloxy having 1 to 9 halogen        atoms; substituted or non-substituted C₃-C₇-cycloalkyl;        C₃-C₇-halogenocycloalkyl having 1 to 9 halogen atoms;        substituted or non-substituted C₄-C₇-cycloalkenyl;        C₄-C₇-halogenocycloalkenyl having 1 to 9 halogen atoms;        substituted or non-substituted (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl;        substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkenyl;        substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkynyl;        substituted or non-substituted tri(C₁-C₈)alkylsilyl; substituted        or non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted        or non-substituted C₁-C₈-alkylcarbonyl;        C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbonyloxy;        C₁-C₈-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbonylamino;        C₁-C₈-halogenoalkylcarbonylamino having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkoxycarbonyl;        C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkyloxycarbonyloxy;        C₁-C₈-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbamoyl; substituted        or non-substituted di-C₁-C₈-alkylcarbamoyl; substituted or        non-substituted C₁-C₈-alkylaminocarbonyloxy; substituted or        non-substituted di-C₁-C₈-alkylaminocarbonyloxy; substituted or        non-substituted N—(C₁-C₈-alkyl)hydroxy carbamoyl; substituted or        non-substituted C₁-C₈-alkoxycarbamoyl; substituted or        non-substituted N—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl that        can be substituted by up to 6 groups Q which can be the same or        different; aryl-C₁-C₈-alkyl that can be substituted by up to 6        groups Q which can be the same or different; aryl-C₂-C₈-alkenyl        that can be substituted by up to 6 groups Q which can be the        same or different; aryl-C₂-C₈-alkynyl that can be substituted by        up to 6 groups Q which can be the same or different; aryloxy        that can be substituted by up to 6 groups Q which can be the        same or different; arylsulfanyl that can be substituted by up to        6 groups Q which can be the same or different; arylamino that        can be substituted by up to 6 groups Q which can be the same or        different; aryl-C₁-C₈-alkyloxy that can be substituted by up to        6 groups Q which can be the same or different;        aryl-C₁-C₈-alkylsulfanyl that can be substituted by up to 6        groups Q which can be the same or different;        aryl-C₁-C₈-alkylamino that can be substituted by up to 6 groups        Q which can be the same or different; pyridinyl which can be        substituted by up to 4 groups Q; pyridinyloxy which can be        substituted by up to 4 groups Q;    -   Y independently represents a halogen atom; cyano; hydroxy;        amino; sulfanyl; substituted or non-substituted C₁-C₈-alkyl;        C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms; substituted or        non-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 9        halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 9        halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 9        halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 9        halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;        substituted or non-substituted di-C₁-C₈-alkylamino; substituted        or non-substituted C₁-C₈-alkylcarbonyl;        C₁-C₃-halogenoalkylcarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkoxycarbonyl;        C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms; aryl        that can be substituted by up to 6 groups Q which can be the        same or different; or    -   Two geminal Y together with the carbon atom to which they are        linked can form a carbonyl group C(═O);    -   Q independently represents a halogen atom, cyano, nitro,        substituted or non-substituted C₁-C₃-alkyl, C₁-C₈-halogenoalkyl        comprising up to 9 halogen atoms that can be the same or        different, substituted or non-substituted C₁-C₈-alkoxy,        C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms that can        be the same or different, substituted or non-substituted        C₁-C₈-alkylsulfanyl, C₁-C₈-halogenoalkylsulfanyl comprising up        to 9 halogen atoms that can be the same or different,        substituted or non-substituted tri(C₁-C₈)alkylsilyl, substituted        or non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl, substituted        or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl, or        substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl;    -   R independently represents hydrogen atom; halogen atom; nitro;        cyano; hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl;        substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;        substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl;        substituted or non-substituted C₁-C₃-alkyl; C₁-C₈-halogenoalkyl        having 1 to 9 halogen atoms; substituted or non-substituted        C₂-C₈-alkenyl; C₂-C₈-halogenoalkenyl having 1 to 9 halogen        atoms; substituted or non-substituted C₂-C₈-alkynyl;        C₂-C₈-halogenoalkynyl having 1 to 9 halogen atoms; substituted        or non-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1        to 9 halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 9        halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 9        halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 9        halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;        substituted or non-substituted di-C₁-C₈-alkylamino; substituted        or non-substituted C₂-C₈-alkenyloxy; substituted or        non-substituted C₃-C₈-alkynyloxy; substituted or non-substituted        C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 9 halogen        atoms; substituted or non-substituted tri(C₁-C₈)alkylsilyl;        substituted or non-substituted C₁-C₈-alkylcarbonyl;        C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkoxycarbonyl;        C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbamoyl; substituted        or non-substituted di-C₁-C₈-alkylcarbamoyl; phenoxy;        phenylsulfanyl; phenylamino; benzyloxy; benzylsulfanyl; or        benzylamino;        as well as its salts, N-oxides, metal complexes, metalloid        complexes and optically active isomers or geometric isomers        thereof.

Unless indicated otherwise, a group or a substituent that is substitutedaccording to the invention can be substituted by one or more of thefollowing groups or atoms: a halogen atom; nitro; hydroxyl; cyano;isonitrile; amino; sulfanyl; a pentafluoro-λ⁶-sulfanyl group; formyl;formyloxy; formylamino; carbamoyl; N-hydroxycarbamoyl; carbamate;(hydroxyimino)-C₁-C₆-alkyl; C₁-C₈-alkyl; a tri(C₁-C₈-alkyl)silyl;C₃-C₈-cycloalkyl; C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; aC₃-C₈-halogenocycloalkyl having 1 to 5 halogen atoms; C₂-C₈-alkenyl;C₂-C₈-alkynyl; C₂-C₈-alkenyloxy; C₂-C₈-alkynyloxy; C₁-C₈-alkylamino;di-C₁-C₈-alkylamino; C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 5halogen atoms; C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1to 5 halogen atoms; C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy having 1to 5 halogen atoms; C₃-C₈-alkynyloxy; C₃-C₈-halogenoalkynyloxy having 1to 5 halogen atoms; C₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonylhaving 1 to 5 halogen atoms; C₁-C₈-alkylcarbamoyl;di-C₁-C₈-alkylcarbamoyl; N—C₁-C₈-alkyloxycarbamoyl;C₁-C₈-alkoxycarbamoyl; N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl; C₁-C₃alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogenatoms; C₁-C₈-alkylcarbonyloxy; C₁-C₈-halogenoalkylcarbonyloxy having 1to 5 halogen atoms; C₁-C₈-alkylcarbonylamino;C₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms;C₁-C₈-alkylaminocarbonyloxy; di-C₁-C₈-alkylaminocarbonyloxy;C₁-C₈-alkyloxycarbonyloxy; C₁-C₈-alkylsulfanyl;C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms;C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogenatoms; C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5halogen atoms; C₁-C₈-alkylaminosulfamoyl; di-C₁-C₈-alkylaminosulfamoyl;(C₁-C₆-alkoxyimino)-C₁-C₆-alkyl; (C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl;(C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl; 2-oxopyrrolidin-1-yl;(benzyloxyimino)-C₁-C₆-alkyl; C₁-C₈-alkoxyalkyl;C₁-C₈-halogenoalkoxyalkyl having 1 to 5 halogen atoms; benzyloxy;benzylsulfanyl; benzylamino; aryloxy; arylsulfanyl or arylamino.

According to the invention, the following generic terms are generallyused with the following meanings:

-   -   halogen means fluorine, chlorine, bromine or iodine,    -   carboxy means —C(═O)OH;    -   carbonyl means —C(═O)—;    -   carbamoyl means —C(═O)N H₂;    -   N-hydroxycarbamoyl means —C(═O)NHOH;    -   S(O) represents a sulfoxide group;    -   S(O)₂ represents a sulfone group;    -   heteroatom means sulfur, nitrogen or oxygen;    -   methylene means the diradical—CH₂—;    -   an alkyl group, an alkenyl group and an alkynyl group as well as        moieties containing these terms, can be linear or branched;    -   halogenated groups, notably haloalkyl, haloalkoxy and cycloalkyl        groups, can comprise up to nine identical or different halogen        atoms;    -   the term “aryl” means phenyl or naphthyl;    -   In the case of an amino group or the amino moiety of any other        amino-containing group, substituted by two substituents that can        be the same or different, the two substituents together with the        nitrogen atom to which they are linked can form a heterocyclyl        group, preferably a 5- to 7-membered heterocyclyl group, that        can be substituted or that can include other hetero atoms, for        example a morpholino group or piperidinyl group.

Any of the compounds of the present invention can exist in one or moreoptical or chiral isomer forms depending on the number of asymmetriccentres in the compound. The invention thus relates equally to all theoptical isomers and to their racemic or scalemic mixtures (the term“scalemic” denotes a mixture of enantiomers in different proportions)and to the mixtures of all the possible stereoisomers, in allproportions. The diastereoisomers and/or the optical isomers can beseparated according to the methods which are known per se by the manordinary skilled in the art.

Any of the compounds of the present invention can also exist in one ormore geometric isomer forms depending on the number of double bonds inthe compound. The invention thus relates equally to all geometricisomers and to all possible mixtures, in all proportions. The geometricisomers can be separated according to general methods, which are knownper se by the man ordinary skilled in the art.

Any of the compounds of the present invention can also exist in one ormore geometric isomer forms depending on the relative position (syn/antior cis/trans) of the substituents of the chain or ring. The inventionthus relates equally to all syn/anti (or cis/trans) isomers and to allpossible syn/anti (or cis/trans) mixtures, in all proportions. Thesyn/anti (or cis/trans) isomers can be separated according to generalmethods, which are known per se by the man ordinary skilled in the art.

Where a compound of the invention can be present in tautomeric form,such a compound is understood hereinabove and hereinbelow also toinclude, where applicable, corresponding tautomeric forms, even whenthese are not specifically mentioned in each case.

Preferred compounds according to the invention are compounds of formula(I) wherein A is selected in the list consisting of:

-   -   a heterocycle of formula (A¹)

wherein:R¹ to R³ that can be the same or different represent a hydrogen atom; ahalogen atom; substituted or non-substituted C₁-C₅-alkyl;C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different; substituted or non-substituted C₁-C₅-alkoxy orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different;

-   -   a heterocycle of formula (A²)

wherein:R⁴ to R⁶ that can be the same or different represent a hydrogen atom; ahalogen atom; substituted or non-substituted C₁-C₅-alkyl;C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different; substituted or non-substituted C₁-C₅-alkoxy orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different;

-   -   a heterocycle of formula (A³)

wherein:R⁷ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; substituted ornon-substituted C₁-C₅-alkoxy or C₁-C₅-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different;R⁸ represents a hydrogen atom or a substituted or non-substitutedC₁-C₅-alkyl;

-   -   a heterocycle of formula (A⁴)

wherein:R⁹ to R¹¹ that can be the same or different represent a hydrogen atom; ahalogen atom; substituted or to non-substituted C₁-C₅-alkyl; amino;substituted or non-substituted C₁-C₅-alkoxy; substituted ornon-substituted C₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkyl comprising upto 9 halogen atoms that can be the same or different orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different;

-   -   a heterocycle of formula (A⁵)

wherein:R¹² and R¹³ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substitutedor non-substituted C₁-C₅-alkoxy; amino; C₁-C₅-halogenoalkyl comprisingup to 9 halogen atoms that can be the same or different orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different;R¹⁴ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₁-C₅-alkoxy; amino; C₁-C₅-halogenoalkyl comprising up to 9 halogenatoms that can be the same or different or C₁-C₅-halogenoalkoxycomprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A⁶)

wherein:R¹⁵ represents a hydrogen atom; a halogen atom; a cyano; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms thatcan be the same or different or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different;R¹⁶ and R¹⁸ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkoxycarbonyl;substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkoxycomprising up to 9 halogen atoms that can be the same or different orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different;R¹⁷ represent a hydrogen atom or substituted or non-substitutedC₁-C₅-alkyl;

-   -   a heterocycle of formula (A⁷)

wherein:R¹⁹ represents a hydrogen atom or a C₁-C₅-alkyl

R²⁰ to R²² that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different;

-   -   a heterocycle of formula (A⁸)

wherein:R²³ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different;R²⁴ represents a hydrogen atom or substituted or non-substitutedC₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different;

-   -   a heterocycle of formula (A⁹)

wherein:R²⁵ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different;R²⁶ represents a hydrogen atom; substituted or non-substitutedC₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different;

-   -   a heterocycle of formula (A¹⁰)

wherein:R²⁷ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; R²⁸ represents ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; C₁-C₅-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different; amino; substituted ornon-substituted C₁-C₅-alkylamino or substituted or non-substituteddi(C₁-C₅-alkyl)amino;

-   -   a heterocycle of formula (A¹¹)

wherein:R²⁹ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms thatcan be the same or different or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different;R³⁰ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; C₁-C₆-halogenoalkoxycomprising up to 9 halogen atoms that can be the same or different;amino; substituted or non-substituted C₁-C₅-alkylamino or substituted ornon-substituted di(C₁-C₅-alkyl)amino;

-   -   a heterocycle of formula (A¹²)

wherein:R³¹ represents a hydrogen atom or a substituted or non-substitutedC₁-C₅-alkylR³² represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different;R³³ represents a hydrogen atom; a halogen atom; a nitro; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms thatcan be the same or different or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A¹³)

wherein:R³⁴ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₃-C₅-cycloalkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atomsthat can be the same or different; substituted or non-substitutedC₁-C₅-alkoxy; substituted or non-substituted C₂-C₅-alkynyloxy orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different; R³⁵ represents a hydrogen atom; a halogen atom;substituted or non-substituted C₁-C₅-alkyl; a cyano; substituted ornon-substituted C₁-C₅-alkoxy; substituted or non-substitutedC₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkyl comprising up to 9 halogenatoms that can be the same or different; C₁-C₅-halogenoalkoxy comprisingup to 9 halogen atoms that can be the same or different; amino;substituted or non-substituted C₁-C₅-alkylamino or substituted ornon-substituted di(C₁-C₅-alkyl)amino; R³⁶ represents a hydrogen atom orsubstituted or non-substituted C₁-C₅-alkyl;

-   -   a heterocycle of formula (A¹⁴)

wherein:R³⁷ and R³⁸ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl;C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different; substituted or non-substituted C₁-C₅-alkoxy or asubstituted or non-substituted C₁-C₅-alkylsulfanyl;R³⁹ represents a hydrogen atom or substituted or non-substitutedC₁-C₅-alkyl;

-   -   a heterocycle of formula (A¹⁵)

wherein:R⁴⁰ and R⁴¹ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different;

-   -   a heterocycle of formula (A¹⁶)

wherein:R⁴² and R⁴³ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl;C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different or amino;

-   -   a heterocycle of formula (A¹⁷)

wherein:R⁴⁴ and R⁴⁵ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different;

-   -   a heterocycle of formula (A¹⁸)

wherein:R⁴⁷ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different;R⁴⁶ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different or substituted ornon-substituted C₁-C₅-alkylsulfanyl;

-   -   a heterocycle of formula (A¹⁹)

wherein:R⁴⁰ and R⁴⁵ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substitutedor non-substituted C₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different or C₁-C₅-halogenoalkylcomprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A²⁰)

wherein:R⁵⁰ and R⁵¹ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substitutedor non-substituted C₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different or C₁-C₅-halogenoalkylcomprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A²¹)

wherein:R⁵² represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different.

-   -   a heterocycle of formula (A²²)

wherein:R⁵³ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different.

-   -   a heterocycle of formula (A²³)

wherein:R⁵⁴ and R⁵⁶ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different;R⁵⁵ represents a hydrogen atom or substituted or non-substitutedC₁-C₆-alkyl;

-   -   a heterocycle of formula (A²⁴)

wherein:R⁵⁷ and R⁵⁹ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different;R⁵⁸ represents a hydrogen atom or substituted or non-substitutedC₁-C₅-alkyl;

-   -   a heterocycle of formula (A²⁵)

wherein:R⁶⁰ and R⁶¹ that can be the same or different represent a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different;R⁶² represents a hydrogen atom or substituted or non-substitutedC₁-C₅-alkyl;

-   -   a heterocycle of formula (A²⁶)

wherein:R⁶⁵ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₃-C₅-cycloalkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atomsthat can be the same or different; substituted or non-substitutedC₁-C₅-alkoxy; substituted or non-substituted C₂-C₅-alkynyloxy orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different; R⁶³ represents a hydrogen atom; a halogen atom;substituted or non-substituted C₁-C₅-alkyl; a cyano; substituted ornon-substituted C₁-C₅-alkoxy; substituted or non-substitutedC₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkyl comprising up to 9 halogenatoms that can be the same or different; C₁-C₅-halogenoalkoxy comprisingup to 9 halogen atoms that can be the same or different; amino;substituted or non-substituted C₁-C₅-alkylamino or di(C₁-C₅-alkyl)amino;R⁶⁴ represents a hydrogen atom or substituted or non-substitutedC₁-C₅-alkyl.

More preferred compounds according to the invention are compounds offormula (I) wherein A is selected in the list consisting of A²; A⁵; A⁶;A¹⁰ and A¹³ as herein-defined.

Even more preferred compounds according to the invention are compoundsof formula (I) wherein A represents A¹³ wherein R³⁴ represents asubstituted or non-substituted C₁-C₅-alkyl, C₁-C₅-halogenoalkylcomprising up to 9 halogen atoms that can be the same or different;substituted or non-substituted C₁-C₅-alkoxy; R³⁵ represents a hydrogenatom or a halogen atom and R³⁶ represents a substituted ornon-substituted C₁-C₅-alkyl.

Even more preferred compounds according to the invention are compoundsof formula (I) wherein A represents A¹³ wherein R³⁴ representsC₁-C₅-alkyl, C₁-C₅-halogenoalkyl comprising up to 3 halogen atoms thatcan be the same or different; R³⁵ represents a hydrogen atom; a chlorineatom; or a fluorine atom; and R³⁶ represents a methyl.

Other preferred compounds according to the invention are compounds offormula (I) wherein T represents O.

Other preferred compounds according to the invention are compounds offormula (I) wherein Z¹ represents a substituted or non-substitutedcyclopropyl.

Other more preferred compounds according to the invention are compoundsof formula (I) wherein Z¹ represents a non-substituted cyclopropyl or a2-C₁-C₅-alkylcyclopropyl.

Other even more preferred compounds according to the invention arecompounds of formula (I) wherein Z¹ represents a non-substitutedcyclopropyl.

Other even more preferred compounds according to the invention arecompounds of formula (I) wherein Z¹ represents a 2-methylcyclopropyl.

Other preferred compounds according to the invention are compounds offormula (I) wherein Z² and Z³ independently represent a hydrogen atom ora C₁-C₈-alkyl, preferably a hydrogen atom or a methyl.

More preferred compounds according to the invention are compounds offormula (I) wherein Z² represents a hydrogen atom and Z³ represents ahydrogen atom or a methyl.

Other preferred compounds according to the invention are compounds offormula (I) wherein n represents 0, 1 or 2.

Other preferred compounds according to the invention are compounds offormula (I) wherein m represents 0, 1, 2 or 3.

Other preferred compounds according to the invention are compounds offormula (I) wherein p represents 2, 3 or 4.

Other preferred compounds according to the invention are compounds offormula (I) wherein X independently, represents a halogen atom;substituted or non substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkylcomprising up to 9 halogen atoms which can be the same or different;substituted or non substituted C₃-C₇-cycloalkyl; tri(C₁-C₈-alkyl)silyl;or substituted or non substituted C₁-C₈-alkylsulfanyl.

Other preferred compounds according to the invention are compounds offormula (I) wherein Y independently, represents a halogen atom;substituted or non substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkylcomprising up to 9 halogen atoms which can be the same or different;substituted or non substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxycomprising up to 9 halogen atoms which can be the same or different.

The above mentioned preferences with regard to the substituents of thecompounds according to the invention can be combined in various manners.These combinations of preferred features thus provide sub-classes ofcompounds according to the invention. Examples of such sub-classes ofpreferred compounds according to the invention are:

-   -   preferred features of A with preferred features of T, Z¹ to Z³,        n, m, p, X and Y;    -   preferred features of T with preferred features of A, Z¹ to Z³,        n, m, p, X and Y;    -   preferred features of Z¹ with preferred features of A, T, Z²,        Z³, n, m, p, X and Y;    -   preferred features of Z² with preferred features of A, T, Z¹,        Z³, n, m, p, X and Y;    -   preferred features of Z³ with preferred features of A, T, Z¹,        Z², n, m, p, X and Y;    -   preferred features of n with preferred features of A, T, Z¹ to        Z³, m, p, X and Y;    -   preferred features of m with preferred features of A, T, Z¹ to        Z³, n, p, X and Y;    -   preferred features of p with preferred features of A, T, Z¹ to        Z³, n, m, X and Y;    -   preferred features of X with preferred features of A, T, Z¹ to        Z³, n, m, p and Y;    -   preferred features of Y with preferred features of A, T, Z¹ to        Z³, n, m, p and X.

In these combinations of preferred features of the substituents of thecompounds according to the invention, the said preferred features canalso be selected among the more preferred features of each of A, T, Z¹to Z³, n, m, p, X and Y so as to form most preferred subclasses ofcompounds according to the invention.

The present invention also relates to a process for the preparation ofthe compound of formula (I). Thus, according to a further aspect of thepresent invention there is provided a process P1 for the preparation ofa compound of formula (I) as herein-defined and wherein T represents Oand that comprises reaction of an amine of formula (II) or one of itssalts:

wherein Z¹, Z², Z³, n, m, p, X and Y are as herein-defined; with acarboxylic acid derivative of formula (III):

wherein A is as herein-defined and L¹ represents a leaving groupselected in the list consisting of a halogen atom, a hydroxyl group,—OR^(a), —OC(═O)R^(a), R^(a) being a substituted or non-substitutedC₁-C₆-alkyl, a substituted or non-substituted C₁-C₆-haloalkyl, a benzyl,4-methoxybenzyl or pentafluorophenyl group, or a group of formulaO—C(═O)A; in the presence of a catalyst and in the presence of acondensing agent in case L¹ represents a hydroxyl group, and in thepresence of an acid binder in case L¹ represents a halogen atom.

N-substituted amine derivatives of formula (II) are known or can beprepared by known processes such as reductive amination of aldehydes orketones (Bioorganics and Medicinal Chemistry Letters (2006), 16, 2014),or reduction of imines (Tetrahedron (2005), 61, 11689), or nucleophilicsubstitution of a halogen, mesylate or tosylate (Journal of MedicinalChemistry (2002), 45, 3887).

Carboxylic acid derivatives of formula (III) are known or can beprepared by known processes.

In case L¹ represents a hydroxy group, process P1 according to thepresent invention is conducted in the presence of condensing agent.Suitable condensing agent may be selected in the non limited listconsisting of acid halide former, such as phosgene, phosphoroustribromide, phosphorous trichloride, phosphorous pentachloride,phosphorous trichloride oxide or thionyl chloride; anhydride former,such as ethyl chloroformate, methyl chloroformate, isopropylchloroformate, isobutyl chloroformate or methanesulfonyl chloride;carbodiimides, such as N,N′-dicyclohexylcarbodiimide (DCC) or othercustomary condensing agents, such as phosphorous pentoxide,polyphosphoric acid, N,N′-carbonyl-diimidazole,2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ),triphenylphosphine/tetrachloro-methane,4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methylmorpholinium chloridehydrate, bromo-tripyrrolidinophosphoniumhexafluorophosphate orpropanephosphonic anhydride (T3P).

Process P1 according to the present invention is conducted in thepresence of a catalyst. Suitable catalyst may be selected in the listconsisting of N,N-dimethylpyridin-4-amine, 1-hydroxy-benzotriazole orN,N-dimethylformamide.

In case L¹ represents a halogen atom, process P1 according to thepresent invention is conducted in the presence of an acid binder.Suitable acid binders for carrying out process P1 according to theinvention are in each case all inorganic and organic bases that arecustomary for such reactions. Preference is given to using alkalineearth metal, alkali metal hydride, alkali metal hydroxides or alkalimetal alkoxides, such as sodium hydroxide, sodium hydride, calciumhydroxide, potassium hydroxide, potassium tert-butoxide or otherammonium hydroxide, alkali metal carbonates, such as caesium carbonate,sodium carbonate, potassium carbonate, potassium bicarbonate, sodiumbicarbonate, alkali metal or alkaline earth metal acetates, such assodium acetate, potassium acetate, calcium acetate and also tertiaryamines, such as trimethylamine, triethylamine, diisopropylethylamine,tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylpyridin-4-amine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU).

It is also possible to work in the absence of an additional condensingagent or to employ an excess of the amine component, so that itsimultaneously acts as acid binder agent.

Suitable solvents for carrying out process P1 according to the inventioncan be customary inert organic solvents. Preference is given to usingoptionally halogenated aliphatic, alicyclic or aromatic hydrocarbons,such as petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene,dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride,dichlorethane or trichlorethane; ethers, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone, orhexamethylphosphoric triamide; alcohols such as methanol, ethanol,propanol, iso-propanol; esters, such as methyl acetate or ethyl acetate,sulfoxides, such as dimethyl sulfoxide, or sulfones, such as sulfolane.

When carrying out process P1 according to the invention, the aminederivative of formula (II) can be employed as its salt, such aschlorhydrate or any other convenient salt.

When carrying out process P1 according to the invention, 1 mole or anexcess of the amine derivative of formula (II) and from 1 to 3 moles ofthe acid binder can be employed per mole of the reagent of formula(III).

It is also possible to employ the reaction components in other ratios.Work-up is carried out by known methods.

According to a further aspect of the present invention, there isprovided a second process P2 for the preparation of a compound offormula (I) as illustrated by the following reaction scheme:

wherein A, T, Z¹, Z², Z³, n, m, p, X and Y are as herein-defined, L²represents a halogen atom such as chlorine, bromine or iodine or canrepresent a triflate group and W represents a hydrogen atom or a boronderivative such as a boronic acid, a boronic ester or a potassiumtrifluoroborate derivative.

Process P2 can be performed in the presence of a transition metalcatalyst such as palladium and if appropriate in the presence of aphosphine ligand or a N-heterocyclic carbene ligand and in the presenceof a base and if appropriate in the presence of a solvent.

Compounds of formula (IV) can be prepared by known processes(WO-2007/087906) and the preparation of compounds of formula (V) is wellknown.

Process P2 according to the invention can be carried out in the presenceof a catalyst, such as a metal salt or complex. Suitable metalderivatives for this purpose are transition metal catalysts such aspalladium. Suitable metal salts or complexes for this purpose are forexample, palladium chloride, palladium acetate,tetrakis(triphenylphosphine)palladium,bis(dibenzylideneacetone)palladium, bis(triphenyl phosphine)palladiumdichloride or 1,1′-bis(diphenylphosphino) ferrocenepalladium(II)chloride.

It is also possible to generate a palladium complex in the reactionmixture by separate addition to the reaction of a palladium salt and aligand or salt, such as triethylphosphine, tri-tert-butylphosphine,tri-tert-butylphosphonium tetrafluoroborate, tricyclohexylphosphine,2-(dicyclohexylphosphine)biphenyl, 2-(di-tert-butylphosphine)biphenyl,2-(dicyclohexylphosphine)-2′-(N,N-dimethylamino)biphenyl,triphenylphosphine, tris-(o-tolyl)phosphine, sodium3-(diphenylphosphino)benzenesulfonate, tris-2-(methoxy-phenyl)phosphine,2,2′-bis(diphenylphosphine)-1,1′-binaphthyl,1,4-bis(diphenylphosphine)butane, 1,2-bis(diphenylphosphine) ethane,1,4-bis(dicyclohexylphosphine)butane,1,2-bis(dicyclohexylphosphine)-ethane, 2-(dicyclohexylphosphine)-2′-(N,N-dimethylamino)-biphenyl,1,1′-bis(diphenylphosphino)-ferrocene,(R)-(+1-[(S)-2-diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine,tris-(2,4-tert-butyl-phenyl)phosphite or1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride.

It is also advantageous to choose the appropriate catalyst and/or ligandfrom commercial catalogues such as “Metal Catalysts for OrganicSynthesis” by Strem Chemicals or “Phosphorous Ligands and Compounds” byStrem Chemicals.

Suitable bases for carrying out process P2 according to the inventioncan be inorganic and organic bases which are customary for suchreactions. Preference is given to using alkaline earth metal or alkalimetal hydroxides, such as sodium hydroxide, calcium hydroxide, potassiumhydroxide or other ammonium hydroxide derivatives; alkaline earth metal,alkali metal or ammonium fluorides such as potassium fluoride, caesiumfluoride or tetrabutylammonium fluoride; alkaline earth metal or alkalimetal carbonates, such as sodium carbonate, potassium carbonate,potassium bicarbonate, sodium bicarbonate or caesium carbonate; alkalimetal or alkaline earth metal acetates, such as sodium acetate,potassium acetate or calcium acetate; alkali metal alcoholates, such aspotassium ter-butoxide or sodium ter-butoxide; alkali metal phosphates,such as tri-potassium phosphate; tertiary amines, such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,N,N-dicyclohexylmethylamine, N-methylpiperidine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU); and alsoaromatic bases, such as pyridine, picolines, lutidines or collidines.

Suitable solvents for carrying out process P2 according to the inventioncan be customary inert organic solvents. Preference is given to usingoptionally halogen atomated aliphatic, alicyclic or aromatichydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene,dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride,dichlorethane or trichlorethane; ethers, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate, sulfoxides, such as dimethyl sulfoxide, or sulfones, such assulfolane.

It can also be advantageous when W represents a boron derivative, tocarry out process P2 according to the invention, with a co-solvent suchas water or an alcohol such as methanol, ethanol, propanol, propanol ort-butanol.

When carrying out process P2 according to the invention, 1 mole or anexcess of compound of formula (V) and from 1 to 5 moles of base and from0.01 to 20 mole percent of a palladium complex can be employed per moleof compound of formula (IV).

It is also possible to employ the reaction components in other ratios.Work-up is carried out by known methods.

According to a further aspect according to the invention, there isprovided a third process P3 for the preparation of a compound of formula(I) wherein T represents S, starting from a compound of formula (I)wherein T represents 0 and illustrated according to the followingreaction scheme:

wherein A, Z¹, Z², Z³, n, m, p, X and Y are as herein-defined.

Process P3 according to the invention is performed in the presence of athionating agent.

Starting amide derivatives of formula (I) wherein T represents 0 can beprepared according to processes P1 and P2.

Suitable thionating agents for carrying out process P2 according to theinvention can be sulfur (S), sulfhydric acid (H₂S), sodium sulfide(Na₂S), sodium hydrosulfide (NaHS), boron trisulfide (B₂S₃),bis(diethylaluminium) sulfide ((AlEt₂)₂S), ammonium sulfide ((NH₄)₂S),phosphorous pentasulfide (P255), Lawesson's reagent(2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide) ora polymer-supported thionating reagent such as described in Journal ofthe Chemical Society, Perkin 1 (2001), 358, in the optionally presenceof a catalytic or stoichiometric or excess amount, quantity of a basesuch as an inorganic and organic base. Preference is given to usingalkali metal carbonates, such as sodium carbonate, potassium carbonate,potassium bicarbonate, sodium bicarbonate; heterocyclic aromatic bases,such as pyridine, picoline, lutidine, collidine; and also tertiaryamines, such as trimethylamine, triethylamine, tributylamine,N,N-dimethylaniline, N,N-dimethylpyridin-4-amine or N-methylpiperidine.

Suitable solvents for carrying out process P3 according to the inventioncan be customary inert organic solvents. Preference is given to usingoptionally halogenated aliphatic, alicyclic or aromatic hydrocarbons,such as petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin, chlorobenzene,dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride,dichlorethane or trichlorethane, ethers, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane, nitriles,such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile, sulfurous solvents, such as sulfolane or carbon disulfide.

When carrying out process P3 according to the invention, 1 mole or anexcess of the sulfur equivalent of the thionating agent and from 1 to 3moles of the base can be employed per mole of the amide reactant (I).

It is also possible to employ the reaction components in other ratios.Work-up is carried out by known methods.

Processes P1, P2 and P3 according to the invention are generally carriedout under atmospheric pressure. It is also possible to operate underelevated or reduced pressure.

When carrying out processes P1, P2 and P3 according to the invention,the reaction temperatures can be varied within a relatively wide range.In general, these processes are carried out at temperatures from 0° C.to 200° C., preferably from 10° C. to 160° C. A way to control thetemperature for the processes according to the invention is to usemicrowave technology.

In general, the reaction mixture is concentrated under reduced pressure.The residue that remains can be freed by known methods, such aschromatography or crystallization, from any impurities that can still bepresent.

Work-up is carried out by customary methods. Generally, the reactionmixture is treated with water and the organic phase is separated offand, after drying, concentrated under reduced pressure. If appropriate,the remaining residue can, be freed by customary methods, such aschromatography, crystallization or distillation, from any impuritiesthat may still be present.

The compound according to the present invention can be preparedaccording to the general processes of preparation described above. Itwill nevertheless be understood that, on the basis of his generalknowledge and of available publications, the skilled worker will be ableto adapt this method according to the specifics of each of thecompounds, which it is desired to synthesize.

Still in a further aspect, the present invention relates to compounds offormula (II) useful as intermediate compounds or materials for theprocess of preparation according to the invention. The present inventionthus provides compounds of formula (IIa) as well as their acceptablesalts:

wherein Z², Z³, n, m, p, X and Y are as herein-defined.

N-cyclopropyl derivatives of formula (IIa) can be prepared according toknown methods.

Preferred compounds of formula (IIa) according to the invention are:

-   N-{1-[2-(cyclopent-1-en-1-yl)phenyl]ethyl}cyclopropanamine-   N-[2-(cyclopent-1-en-1-yl)benzyl]cyclopropanamine-   N-[5-chloro-2-(cyclopent-1-en-yl)benzyl]cyclopropanamine-   N-{1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethyl}cyclopropanamine-   N-[2-chloro-5-(cyclopent-1-en-yl)benzyl]cyclopropanamine-   N-[2-(cyclohex-1-en-yl)benzyl]cyclopropanamine-   N-[5-chloro-2-(cyclohex-1-en-1-yl)benzyl]cyclopropanamine-   N-[2-chloro-5-(cyclohex-1-en-1-yl)benzyl]cyclopropanamine-   N-[2-(cyclohept-1-en-1-yl)benzyl]cyclopropanamine-   N-[5-chloro-2-(cyclohept-1-en-yl)benzyl]cyclopropanamine.

In a further aspect, the present invention also relates to a fungicidecomposition comprising an effective and non-phytotoxic amount of anactive compound of formula (I).

The expression “effective and non-phytotoxic amount” means an amount ofcomposition according to the invention that is sufficient to control ordestroy the fungi present or liable to appear on the cropsand that doesnot entail any appreciable symptom of phytotoxicity for the said crops.Such an amount can vary within a wide range depending on the fungus tobe controlled, the type of crop, the climatic conditions and thecompounds included in the fungicide composition according to theinvention. This amount can be determined by systematic field trials thatare within the capabilities of a person skilled in the art.

Thus, according to the invention, there is provided a fungicidecomposition comprising, as an active ingredient, an effective amount ofa compound of formula (I) as herein defined and an agriculturallyacceptable support, carrier or filler.

According to the invention, the term “support” denotes a natural orsynthetic, organic or inorganic compound with that the active compoundof formula (I) is combined or associated to make it easier to apply,notably to the parts of the plant. This support is thus generally inertand should be agriculturally acceptable. The support can be a solid or aliquid. Examples of suitable supports include clays, natural orsynthetic silicates, silica, resins, waxes, solid fertilisers, water,alcohols, in particular butanol, organic solvents, mineral and plantoils and derivatives thereof. Mixtures of such supports can also beused.

The composition according to the invention can also comprise additionalcomponents. In particular, the composition can further comprise asurfactant. The surfactant can be an emulsifier, a dispersing agent or awetting agent of ionic or non-ionic type or a mixture of suchsurfactants. Mention can be made, for example, of polyacrylic acidsalts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonicacid salts, polycondensates of ethylene oxide with fatty alcohols orwith fatty acids or with fatty amines, substituted phenols (inparticular alkylphenols or arylphenols), salts of sulfosuccinic acidesters, taurine derivatives (in particular alkyl taurates), phosphoricesters of polyoxyethylated alcohols or phenols, fatty acid esters ofpolyolsand derivatives of the above compounds containing sulfate,sulfonate and phosphate functions. The presence of at least onesurfactant is generally essential when the active compound and/or theinert support are water-insoluble and when the vector agent for theapplication is water. Preferably, surfactant content can be comprisedfrom 5% to 40% by weight of the composition.

Optionally, additional components can also be included, e.g. protectivecolloids, adhesives, thickeners, thixotropic agents, penetration agents,stabilisers, sequestering agents. More generally, the active compoundscan be combined with any solid or liquid additive, that complies withthe usual formulation techniques.

In general, the composition according to the invention can contain from0.05 to 99% by weight of active compound, preferably 10 to 70% byweight.

Compositions according to the invention can be used in various forms andformulations such as aerosol dispenser, capsule suspension, cold foggingconcentrate, dustable powder, emulsifiable concentrate, emulsion oil inwater, emulsion water in oil, encapsulated granule, fine granule,flowable concentrate for seed treatment, gas (under pressure), gasgenerating product, granule, hot fogging concentrate, macrogranule,microgranule, oil dispersible powder, oil miscible flowable concentrate,oil miscible liquid, paste, plant rodlet, powder for dry seed treatment,seed coated with a pesticide, soluble concentrate, soluble powder,solution for seed treatment, suspension concentrate (flowableconcentrate), ultra low volume (ULV) liquid, ultra low volume (ULV)suspension, water dispersible granules or tablets, water dispersiblepowder for slurry treatment, water soluble granules or tablets, watersoluble powder for seed treatment and wettable powder. Thesecompositions include not only compositions that are ready to be appliedto the plant or seed to be treated by means of a suitable device, suchas a spraying or dusting device, but also concentrated commercialcompositions that must be diluted before application to the crop.

The formulations can be prepared in a manner known per se, for exampleby mixing the active ingredients with at least one customary extender,solvent or diluent, adjuvant, emulsifier, dispersant, and/or binder orfixative, wetting agent, water repellent, if appropriate desiccants andUV stabilizers and, if appropriate, dyes and pigments, antifoams,preservatives, inorganic and organic thickeners, adhesives, gibberellinsand also further processing auxiliaries and also water. Depending on theformulation type to be prepared further processing steps are necessary,e.g. wet grinding, dry grinding and granulation.

The inventive active ingredients may be present as such or in their(commercial) formulations and in the use forms prepared from theseformulations as a mixture with other (known) active ingredients, such asinsecticides, attractants, sterilants, bactericides, acaricides,nematicides, fungicides, growth regulators, herbicides, fertilizers,safeners and/or semiochemicals.

The compounds of formula (I) and the fungicide composition according tothe invention can be used to curatively or preventively control thephytopathogenic fungi of plants or crops.

Thus, according to a further aspect of the invention, there is provideda method for curatively or preventively controlling the phytopathogenicfungi of plants or crops characterised in that a compound of formula (I)or a fungicide composition according to the invention is applied to theseed, the plant or to the fruit of the plant or to the soil wherein theplant is growing or wherein it is desired to grow.

The method of treatment according to the invention can also be useful totreat propagation material such as tubers or rhizomes, but also seeds,seedlings or seedlings pricking out and plants or plants pricking out.This method of treatment can also be useful to treat roots. The methodof treatment according to the invention can also be useful to treat theoverground parts of the plant such as trunks, stems or stalks, leaves,flowers and fruit of the concerned plant.

According to the invention all plants and plant parts can be treated. Byplants is meant all plants and plant populations such as desirable andundesirable wild plants, cultivars and plant varieties (whether or notprotectable by plant variety or plant breeder's rights). Cultivars andplant varieties can be plants obtained by conventional propagation andbreeding methods which can be assisted or supplemented by one or morebiotechnological methods such as by use of double haploids, protoplastfusion, random and directed mutagenesis, molecular or genetic markers orby bioengineering and genetic engineering methods. By plant parts ismeant all above ground and below ground parts and organs of plants suchas shoot, leaf, blossom and root, whereby for example leaves, needles,stems, branches, blossoms, fruiting bodies, fruits and seed as well asroots, corms and rhizomes are listed. Crops and vegetative andgenerative propagating material, for example cuttings, corms, rhizomes,runners and seeds also belong to plant parts.

Among the plants that can be protected by the method according to theinvention, mention may be made of major field crops like corn, soybean,cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassicarapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat,sugarbeet, sugarcane, oats, rye, barley, millet, triticale, flax, vineand various fruits and vegetables of various botanical taxa such asRosaceae sp. (for instance pip fruit such as apples and pears, but alsostone fruit such as apricots, cherries, almonds and peaches, berryfruits such as strawberries), Ribesioidae sp., Juglandaceae sp.,Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceaesp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for instance bananatrees and plantings), Rubiaceae sp. (for instance coffee), Theaceae sp.,Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges andgrapefruit); Solanaceae sp. (for instance tomatoes, potatoes, peppers,eggplant), Liliaceae sp., Compositiae sp. (for instance lettuce,artichoke and chicory—including root chicory, endive or common chicory),Umbelliferae sp. (for instance carrot, parsley, celery and celeriac),Cucurbitaceae sp. (for instance cucumber—including pickling cucumber,squash, watermelon, gourds and melons), Alliaceae sp. (for instanceonions and leek), Cruciferae sp. (for instance white cabbage, redcabbage, broccoli, cauliflower, brussel sprouts, pak choi, kohlrabi,radish, horseradish, cress, Chinese cabbage), Leguminosae sp. (forinstance peanuts, peas and beans beans—such as climbing beans and broadbeans), Chenopodiaceae sp. (for instance mangold, spinach beet, spinach,beetroots), Malvaceae (for instance okra), Asparagaceae (for instanceasparagus); horticultural and forest crops; ornamental plants; as wellas genetically modified homologues of these crops.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants ofwhich a heterologous gene has been stably integrated into genome. Theexpression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for example,antisense technology, cosuppression technology or RNAinterference—RNAi-technology). A heterologous gene that is located inthe genome is also called a transgene. A transgene that is defined byits particular location in the plant genome is called a transformationor transgenic event.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active compounds and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf color, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are also suitable for mobilizing the defense system ofthe plant against attack by unwanted microorganisms. This may, ifappropriate, be one of the reasons of the enhanced activity of thecombinations according to the invention, for example against fungi.Plant-strengthening (resistance-inducing) substances are to beunderstood as meaning, in the present context, those substances orcombinations of substances which are capable of stimulating the defensesystem of plants in such a way that, when subsequently inoculated withunwanted microorganisms, the treated plants display a substantial degreeof resistance to these microorganisms. In the present case, unwantedmicroorganisms are to be understood as meaning phytopathogenic fungi,bacteria and viruses. Thus, the substances according to the inventioncan be employed for protecting plants against attack by theabovementioned pathogens within a certain period of time after thetreatment. The period of time within which protection is effectedgenerally extends from 1 to 10 days, preferably 1 to 7 days, after thetreatment of the plants with the active compounds.

Plants and plant cultivars which are preferably to be treated accordingto the invention include all plants which have genetic material whichimpart particularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants show a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode resistant plants are described in e.g. U.S. patentapplication Ser. Nos. 11/765,491, 11/765,494, 10/926,819, 10/782,020,12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808,12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335,11/763,947, 12/252,453, 12/209,354, 12/491,396 or 12/497,221.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, flooding,increased soil salinity, increased mineral exposure, ozone exposure,high light exposure, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to theinvention, are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including but not limited to, early flowering, floweringcontrol for hybrid seed production, seedling vigor, plant size,internode number and distance, root growth, seed size, fruit size, podsize, pod or ear number, seed number per pod or ear, seed mass, enhancedseed filling, reduced seed dispersal, reduced pod dehiscence and lodgingresistance. Further yield traits include seed composition, such ascarbohydrate content, protein content, oil content and composition,nutritional value, reduction in anti-nutritional compounds, improvedprocessability and better storage stability.

Examples of plants with the above-mentioned traits are non-exhaustivelylisted in Table A.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristic of heterosis or hybrid vigorwhich results in generally higher yield, vigor, health and resistancetowards biotic and abiotic stresses). Such plants are typically made bycrossing an inbred male-sterile parent line (the female parent) withanother inbred male-fertile parent line (the male parent). Hybrid seedis typically harvested from the male sterile plants and sold to growers.Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling, i.e. the mechanical removal of the male reproductive organs(or males flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plantsit is typically useful to ensure that male fertility in the hybridplants is fully restored. This can be accomplished by ensuring that themale parents have appropriate fertility restorer genes which are capableof restoring the male fertility in hybrid plants that contain thegenetic determinants responsible for male-sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO05/002324, WO 06/021972 and U.S. Pat. No. 6,229,072). However, geneticdeterminants for male sterility can also be located in the nucleargenome. Male sterile plants can also be obtained by plant biotechnologymethods such as genetic engineering. A particularly useful means ofobtaining male-sterile plants is described in WO 89/10396 in which, forexample, a ribonuclease such as barnase is selectively expressed in thetapetum cells in the stamens. Fertility can then be restored byexpression in the tapetum cells of a ribonuclease inhibitor such asbarstar (e.g. WO 91/02069).

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-resistant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.Plants can be made tolerant to glyphosate through different means. Forexample, glyphosate-tolerant plants can be obtained by transforming theplant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphatesynthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutantCT7) of the bacterium Salmonella typhimurium (Comai et al., 1983,Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp.(Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genesencoding a Petunia EPSPS (Shah et al., 1986, Science 233, 478-481), aTomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289), or anEleusine EPSPS (WO 01/66704). It can also be a mutated EPSPS asdescribed in for example EP 0837944, WO 00/66746, WO 00/66747 orWO02/26995. Glyphosate-tolerant plants can also be obtained byexpressing a gene that encodes a glyphosate oxido-reductase enzyme asdescribed in U.S. Pat. Nos. 5,776,760 and 5,463,175. Glyphosate-tolerantplants can also be obtained by expressing a gene that encodes aglyphosate acetyl transferase enzyme as described in for example WO02/36782, WO 03/092360, WO 05/012515 and WO 07/024782.Glyphosate-tolerant plants can also be obtained by selecting plantscontaining naturally-occurring mutations of the above-mentioned genes,as described in for example WO 01/024615 or WO 03/013226. Plantsexpressing EPSPS genes that confer glyphosate tolerance are described ine.g. U.S. patent application Ser. Nos. 11/517,991, 10/739,610,12/139,408, 12/352,532, 11/312,866, 11/315,678, 12/421,292, 11/400,598,11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, 11/762,526,11/769,327, 11/769,255, 11/943801 or 12/362,774. Plants comprising othergenes that confer glyphosate tolerance, such as decarboxylase genes, aredescribed in e.g. U.S. patent application Ser. Nos. 11/588,811,11/185,342, 12/364,724, 11/185,560 or 12/423,926.

Other herbicide resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition, e.g. described in U.S.patent application Ser. No. 11/760,602. One such efficient detoxifyingenzyme is an enzyme encoding a phosphinothricin acetyltransferase (suchas the bar or pat protein from Streptomyces species). Plants expressingan exogenous phosphinothricin acetyltransferase are for exampledescribed in U.S. Pat. Nos. 5,561,236; 5,648,477; 5,646,024; 5,273,894;5,637,489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze thereaction in which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD-inhibitors can be transformedwith a gene encoding a naturally-occurring resistant HPPD enzyme, or agene encoding a mutated or chimeric HPPD enzyme as described in WO96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387, orU.S. Pat. No. 6,768,044. Tolerance to HPPD-inhibitors can also beobtained by transforming plants with genes encoding certain enzymesenabling the formation of homogentisate despite the inhibition of thenative HPPD enzyme by the HPPD-inhibitor. Such plants and genes aredescribed in WO 99/34008 and WO 02/36787. Tolerance of plants to HPPDinhibitors can also be improved by transforming plants with a geneencoding an enzyme having prephenate deshydrogenase (PDH) activity inaddition to a gene encoding an HPPD-tolerant enzyme, as described in WO2004/024928. Further, plants can be made more tolerant to HPPD-inhibitorherbicides by adding into their genome a gene encoding an enzyme capableof metabolizing or degrading HPPD inhibitors, such as the CYP450 enzymesshown in WO 2007/103567 and WO 2008/150473.

Still further herbicide resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitorsinclude, for example, sulfonylurea, imidazolinone, triazolopyrimidines,pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides, as described for examplein Tranel and Wright (2002, Weed Science 50:700-712), but also, in U.S.Pat. Nos. 5,605,011, 5,378,824, 5,141,870, and 5,013,659. The productionof sulfonylurea-tolerant plants and imidazolinone-tolerant plants isdescribed in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870; 5,767,361;5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and 5,378,824;and international publication WO 96/33270. Other imidazolinone-tolerantplants are also described in for example WO 2004/040012, WO 2004/106529,WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO2006/024351, and WO 2006/060634. Further sulfonylurea- andimidazolinone-tolerant plants are also described in for example WO07/024782 and US Patent Application No. 61/288,958.

Other plants tolerant to imidazolinone and/or sulfonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding as described for examplefor soybeans in U.S. Pat. No. 5,084,082, for rice in WO 97/41218, forsugar beet in U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce inU.S. Pat. No. 5,198,599, or for sunflower in WO 01/065922.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

-   -   1) an insecticidal crystal protein from Bacillus thuringiensis        or an insecticidal portion thereof, such as the insecticidal        crystal proteins listed by Crickmore et al. (1998, Microbiology        and Molecular Biology Reviews, 62: 807-813), updated by        Crickmore et al. (2005) at the Bacillus thuringiensis toxin        nomenclature, online at:    -   http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or        insecticidal portions thereof, e.g., proteins of the Cry protein        classes Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab,        Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP        1999141 and WO 2007/107302), or such proteins encoded by        synthetic genes as e.g. described in and U.S. patent application        Ser. No. 12/249,016; or    -   2) a crystal protein from Bacillus thuringiensis or a portion        thereof which is insecticidal in the presence of a second other        crystal protein from Bacillus thuringiensis or a portion        thereof, such as the binary toxin made up of the Cry34 and Cry35        crystal proteins (Moellenbeck et al. 2001, Nat. Biotechnol. 19:        668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71,        1765-1774) or the binary toxin made up of the Cry1A or Cry1F        proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.        patent application Ser. No. 12/214,022 and EP 08010791.5); or    -   3) a hybrid insecticidal protein comprising parts of different        insecticidal crystal proteins from Bacillus thuringiensis, such        as a hybrid of the proteins of 1) above or a hybrid of the        proteins of 2) above, e.g., the Cry1A.105 protein produced by        corn event MON89034 (WO 2007/027777); or    -   4) a protein of any one of 1) to 3) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes introduced into the        encoding DNA during cloning or transformation, such as the        Cry3Bb1 protein in corn events MON863 or MON88017, or the Cry3A        protein in corn event MIR604; or    -   5) an insecticidal secreted protein from Bacillus thuringiensis        or Bacillus cereus, or an insecticidal portion thereof, such as        the vegetative insecticidal (VIP) proteins listed at:    -   http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html,        e.g., proteins from the VIP3Aa protein class; or    -   6) a secreted protein from Bacillus thuringiensis or Bacillus        cereus which is insecticidal in the presence of a second        secreted protein from Bacillus thuringiensis or B. cereus, such        as the binary toxin made up of the VIP1A and VIP2A proteins (WO        94/21795); or    -   7) a hybrid insecticidal protein comprising parts from different        secreted proteins from Bacillus thuringiensis or Bacillus        cereus, such as a hybrid of the proteins in 1) above or a hybrid        of the proteins in 2) above; or    -   8) a protein of any one of 5) to 7) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes introduced into the        encoding DNA during cloning or transformation (while still        encoding an insecticidal protein), such as the VIP3Aa protein in        cotton event COT102; or    -   9) a secreted protein from Bacillus thuringiensis or Bacillus        cereus which is insecticidal in the presence of a crystal        protein from Bacillus thuringiensis, such as the binary toxin        made up of VIP3 and Cry1A or Cry1F (US Patent Appl. No.        61/126,083 and 61/195,019), or the binary toxin made up of the        VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.        patent application Ser. No. 12/214,022 and EP 08010791.5).    -   10) a protein of 9) above wherein some, particularly 1 to 10,        amino acids have been replaced by another amino acid to obtain a        higher insecticidal activity to a target insect species, and/or        to expand the range of target insect species affected, and/or        because of changes introduced into the encoding DNA during        cloning or transformation (while still encoding an insecticidal        protein)

Of course, an insect-resistant transgenic plant, as used herein, alsoincludes any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 10. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 10, to expand the range oftarget insect species affected when using different proteins directed atdifferent target insect species, or to delay insect resistancedevelopment to the plants by using different proteins insecticidal tothe same target insect species but having a different mode of action,such as binding to different receptor binding sites in the insect.

An “insect-resistant transgenic plant”, as used herein, further includesany plant containing at least one transgene comprising a sequenceproducing upon expression a double-stranded RNA which upon ingestion bya plant insect pest inhibits the growth of this insect pest, asdescribed e.g. in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

-   -   1) plants which contain a transgene capable of reducing the        expression and/or the activity of poly(ADP-ribose) polymerase        (PARP) gene in the plant cells or plants as described in WO        00/04173, WO/2006/045633, EP 04077984.5, or EP 06009836.5.    -   2) plants which contain a stress tolerance enhancing transgene        capable of reducing the expression and/or the activity of the        PARG encoding genes of the plants or plants cells, as described        e.g. in WO 2004/090140.    -   3) plants which contain a stress tolerance enhancing transgene        coding for a plant-functional enzyme of the nicotineamide        adenine dinucleotide salvage synthesis pathway including        nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic        acid mononucleotide adenyl transferase, nicotinamide adenine        dinucleotide synthetase or nicotine amide        phosphorybosyltransferase as described e.g. in EP 04077624.7, WO        2006/133827, PCT/EP07/002433, EP 1999263, or WO 2007/107326.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

-   -   1) transgenic plants which synthesize a modified starch, which        in its physical-chemical characteristics, in particular the        amylose content or the amylose/amylopectin ratio, the degree of        branching, the average chain length, the side chain        distribution, the viscosity behaviour, the gelling strength, the        starch grain size and/or the starch grain morphology, is changed        in comparison with the synthesised starch in wild type plant        cells or plants, so that this is better suited for special        applications. Said transgenic plants synthesizing a modified        starch are disclosed, for example, in EP 0571427, WO 95/04826,        EP 0719338, WO 96/15248, WO 96/19581, WO 96/27674, WO 97/11188,        WO 97/26362, WO 97/32985, WO 97/42328, WO 97/44472, WO 97/45545,        WO 98/27212, WO 98/40503, WO99/58688, WO 99/58690, WO 99/58654,        WO 00/08184, WO 00/08185, WO 00/08175, WO 00/28052, WO 00/77229,        WO 01/12782, WO 01/12826, WO 02/101059, WO 03/071860, WO        2004/056999, WO 2005/030942, WO 2005/030941, WO 2005/095632, WO        2005/095617, WO 2005/095619, WO 2005/095618, WO 2005/123927, WO        2006/018319, WO 2006/103107, WO 2006/108702, WO 2007/009823, WO        00/22140, WO 2006/063862, WO 2006/072603, WO 02/034923, EP        06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1, EP        07090009.7, WO 01/14569, WO 02/79410, WO 03/33540, WO        2004/078983, WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145,        WO 99/12950, WO 99/66050, WO 99/53072, U.S. Pat. No. 6,734,341,        WO 00/11192, WO 98/22604, WO 98/32326, WO 01/98509, WO 01/98509,        WO 2005/002359, U.S. Pat. No. 5,824,790, U.S. Pat. No.        6,013,861, WO 94/04693, WO 94/09144, WO 94/11520, WO 95/35026,        WO 97/20936    -   2) transgenic plants which synthesize non starch carbohydrate        polymers or which synthesize non starch carbohydrate polymers        with altered properties in comparison to wild type plants        without genetic modification. Examples are plants producing        polyfructose, especially of the inulin and levan-type, as        disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460,        and WO 99/24593, plants producing alpha-1,4-glucans as disclosed        in WO 95/31553, US 2002031826, U.S. Pat. No. 6,284,479, U.S.        Pat. No. 5,712,107, WO 97/47806, WO 97/47807, WO 97/47808 and WO        00/14249, plants producing alpha-1,6 branched alpha-1,4-glucans,        as disclosed in WO 00/73422, plants producing alternan, as        disclosed in e.g. WO 00/47727, WO 00/73422, EP 06077301.7, U.S.        Pat. No. 5,908,975 and EP 0728213,    -   3) transgenic plants which produce hyaluronan, as for example        disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO        2007/039316, JP 2006304779, and WO 2005/012529.    -   4) transgenic plants or hybrid plants, such as onions with        characteristics such as ‘high soluble solids content’, low        pungency′ (LP) and/or ‘long storage’ (LS), as described in U.S.        patent application Ser. No. 12/020,360 and 61/054,026.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants contain a mutation imparting such alteredfiber characteristics and include:

-   -   a) Plants, such as cotton plants, containing an altered form of        cellulose synthase genes as described in WO 98/00549    -   b) Plants, such as cotton plants, containing an altered form of        rsw2 or rsw3 homologous nucleic acids as described in WO        2004/053219    -   c) Plants, such as cotton plants, with increased expression of        sucrose phosphate synthase as described in WO 01/17333    -   d) Plants, such as cotton plants, with increased expression of        sucrose synthase as described in WO 02/45485    -   e) Plants, such as cotton plants, wherein the timing of the        plasmodesmatal gating at the basis of the fiber cell is altered,        e.g. through downregulation of fiber-selective β-1,3-glucanase        as described in WO 2005/017157, or as described in EP 08075514.3        or U.S. Patent Appl. No. 61/128,938    -   f) Plants, such as cotton plants, having fibers with altered        reactivity, e.g. through the expression of        N-acetylglucosaminetransferase gene including nodC and chitin        synthase genes as described in WO 2006/136351

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered oil profile characteristics and include:

-   -   a) Plants, such as oilseed rape plants, producing oil having a        high oleic acid content as described e.g. in U.S. Pat. No.        5,969,169, U.S. Pat. No. 5,840,946 or U.S. Pat. No. 6,323,392 or        U.S. Pat. No. 6,063,947    -   b) Plants such as oilseed rape plants, producing oil having a        low linolenic acid content as described in U.S. Pat. No.        6,270,828, U.S. Pat. No. 6,169,190, or U.S. Pat. No. 5,965,755    -   c) Plant such as oilseed rape plants, producing oil having a low        level of saturated fatty acids as described e.g. in U.S. Pat.        No. 5,434,283 or U.S. patent application Ser. No. 12/668,303

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered seed shattering characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered seed shattering characteristics andinclude plants such as oilseed rape plants with delayed or reduced seedshattering as described in U.S. Patent Appl. No. 61/135,230 WO09/068313and WO10/006732.

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, orcombination of transformation events, that are the subject of petitionsfor nonregulated status, in the United States of America, to the Animaland Plant Health Inspection Service (APHIS) of the United StatesDepartment of Agriculture (USDA) whether such petitions are granted orare still pending. At any time this information is readily availablefrom APHIS (4700 River Road Riverdale, Md. 20737, USA), for instance onits internet site (URL http://www.aphis.usda.gov/brs/not_reg.html). Onthe filing date of this application the petitions for nonregulatedstatus that were pending with APHIS or granted by APHIS were thoselisted in table B which contains the following information:

-   -   Petition: the identification number of the petition. Technical        descriptions of the transformation events can be found in the        individual petition documents which are obtainable from APHIS,        for example on the APHIS website, by reference to this petition        number. These descriptions are herein incorporated by reference.    -   Extension of Petition: reference to a previous petition for        which an extension is requested.    -   Institution: the name of the entity submitting the petition.    -   Regulated article: the plant species concerned.    -   Transgenic phenotype: the trait conferred to the plants by the        transformation event.    -   Transformation event or line: the name of the event or events        (sometimes also designated as lines or lines) for which        nonregulated status is requested.    -   APHIS documents: various documents published by APHIS in        relation to the Petition and which can be requested with APHIS.

Additional particularly useful plants containing single transformationevents or combinations of transformation events are listed for examplein the databases from various national or regional regulatory agencies(see for example http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php). Particularly useful transgenic plantswhich may be treated according to the invention are plants containingtransformation events, or a combination of transformation events, andthat are listed for example in the databases for various national orregional regulatory agencies including Event 1143-14A (cotton, insectcontrol, not deposited, described in WO 2006/128569); Event 1143-51B(cotton, insect control, not deposited, described in WO 2006/128570);Event 1445 (cotton, herbicide tolerance, not deposited, described inUS-A 2002-120964 or WO 02/034946); Event 17053 (rice, herbicidetolerance, deposited as PTA-9843, described in WO 2010/117737); Event17314 (rice, herbicide tolerance, deposited as PTA-9844, described in WO2010/117735); Event 281-24-236 (cotton, insect control—herbicidetolerance, deposited as PTA-6233, described in WO 2005/103266 or US-A2005-216969); Event 3006-210-23 (cotton, insect control—herbicidetolerance, deposited as PTA-6233, described in US-A 2007-143876 or WO2005/103266); Event 3272 (corn, quality trait, deposited as PTA-9972,described in WO 2006/098952 or US-A 2006-230473); Event 40416 (corn,insect control—herbicide tolerance, deposited as ATCC PTA-11508,described in WO 2011/075593); Event 43A47 (corn, insectcontrol—herbicide tolerance, deposited as ATCC PTA-11509, described inWO 2011/075595); Event 5307 (corn, insect control, deposited as ATCCPTA-9561, described in WO 2010/077816); Event ASR-368 (bent grass,herbicide tolerance, deposited as ATCC PTA-4816, described in US-A2006-162007 or WO 2004/053062); Event B16 (corn, herbicide tolerance,not deposited, described in US-A 2003-126634); Event BPS-CV127-9(soybean, herbicide tolerance, deposited as NCIMB No. 41603, describedin WO 2010/080829); Event CE43-67B (cotton, insect control, deposited asDSM ACC2724, described in US-A 2009-217423 or WO2006/128573); EventCE44-69D (cotton, insect control, not deposited, described in US-A2010-0024077); Event CE44-69D (cotton, insect control, not deposited,described in WO 2006/128571); Event CE46-02A (cotton, insect control,not deposited, described in WO 2006/128572); Event COT102 (cotton,insect control, not deposited, described in US-A 2006-130175 or WO2004/039986); Event COT202 (cotton, insect control, not deposited,described in US-A 2007-067868 or WO 2005/054479); Event COT203 (cotton,insect control, not deposited, described in WO 2005/054480); EventDAS40278 (corn, herbicide tolerance, deposited as ATCC PTA-10244,described in WO 2011/022469); Event DAS-59122-7 (corn, insectcontrol—herbicide tolerance, deposited as ATCC PTA 11384, described inUS-A 2006-070139); Event DAS-59132 (corn, insect control—herbicidetolerance, not deposited, described in WO 2009/100188); Event DAS68416(soybean, herbicide tolerance, deposited as ATCC PTA-10442, described inWO 2011/066384 or WO 2011/066360); Event DP-098140-6 (corn, herbicidetolerance, deposited as ATCC PTA-8296, described in US-A 2009-137395 orWO 2008/112019); Event DP-305423-1 (soybean, quality trait, notdeposited, described in US-A 2008-312082 or WO 2008/054747); EventDP-32138-1 (corn, hybridization system, deposited as ATCC PTA-9158,described in US-A 2009-0210970 or WO 2009/103049); Event DP-356043-5(soybean, herbicide tolerance, deposited as ATCC PTA-8287, described inUS-A 2010-0184079 or WO 2008/002872); Event EE-1 (brinjal, insectcontrol, not deposited, described in WO 2007/091277); Event FI117 (corn,herbicide tolerance, deposited as ATCC 209031, described in US-A2006-059581 or WO 98/044140); Event GA21 (corn, herbicide tolerance,deposited as ATCC 209033, described in US-A 2005-086719 or WO98/044140); Event GG25 (corn, herbicide tolerance, deposited as ATCC209032, described in US-A 2005-188434 or WO 98/044140); Event GHB119(cotton, insect control—herbicide tolerance, deposited as ATCC PTA-8398,described in WO 2008/151780); Event GHB614 (cotton, herbicide tolerance,deposited as ATCC PTA-6878, described in US-A 2010-050282 or WO2007/017186); Event GJ11 (corn, herbicide tolerance, deposited as ATCC209030, described in US-A 2005-188434 or WO 98/044140); Event GM RZ13(sugar beet, virus resistance, deposited as NCIMB-41601, described in WO2010/076212); Event H7-1 (sugar beet, herbicide tolerance, deposited asNCIMB 41158 or NCIMB 41159, described in US-A 2004-172669 or WO2004/074492); Event JOPLIN1 (wheat, disease tolerance, not deposited,described in US-A 2008-064032); Event LL27 (soybean, herbicidetolerance, deposited as NCIMB41658, described in WO 2006/108674 or US-A2008-320616); Event LL55 (soybean, herbicide tolerance, deposited asNCIMB 41660, described in WO 2006/108675 or US-A 2008-196127); EventLLcotton25 (cotton, herbicide tolerance, deposited as ATCC PTA-3343,described in WO 03/013224 or US-A 2003-097687); Event LLRICE06 (rice,herbicide tolerance, deposited as ATCC-23352, described in U.S. Pat. No.6,468,747 or WO 00/026345); Event LLRICE601 (rice, herbicide tolerance,deposited as ATCC PTA-2600, described in US-A 2008-2289060 or WO00/026356); Event LY038 (corn, quality trait, deposited as ATCCPTA-5623, described in US-A 2007-028322 or WO 2005/061720); Event MIR162(corn, insect control, deposited as PTA-8166, described in US-A2009-300784 or WO 2007/142840); Event MIR604 (corn, insect control, notdeposited, described in US-A 2008-167456 or WO 2005/103301); EventMON15985 (cotton, insect control, deposited as ATCC PTA-2516, describedin US-A 2004-250317 or WO 02/100163); Event MON810 (corn, insectcontrol, not deposited, described in US-A 2002-102582); Event MON863(corn, insect control, deposited as ATCC PTA-2605, described in WO2004/011601 or US-A 2006-095986); Event MON87427 (corn, pollinationcontrol, deposited as ATCC PTA-7899, described in WO 2011/062904); EventMON87460 (corn, stress tolerance, deposited as ATCC PTA-8910, describedin WO 2009/111263 or US-A 2011-0138504); Event MON87701 (soybean, insectcontrol, deposited as ATCC PTA-8194, described in US-A 2009-130071 or WO2009/064652); Event MON87705 (soybean, quality trait—herbicidetolerance, deposited as ATCC PTA-9241, described in US-A 2010-0080887 orWO 2010/037016); Event MON87708 (soybean, herbicide tolerance, depositedas ATCC PTA9670, described in WO 2011/034704); Event MON87754 (soybean,quality trait, deposited as ATCC PTA-9385, described in WO 2010/024976);Event MON87769 (soybean, quality trait, deposited as ATCC PTA-8911,described in US-A 2011-0067141 or WO 2009/102873); Event MON88017 (corn,insect control—herbicide tolerance, deposited as ATCC PTA-5582,described in US-A 2008-028482 or WO 2005/059103); Event MON88913(cotton, herbicide tolerance, deposited as ATCC PTA-4854, described inWO 2004/072235 or US-A 2006-059590); Event MON89034 (corn, insectcontrol, deposited as ATCC PTA-7455, described in WO 2007/140256 or US-A2008-260932); Event MON89788 (soybean, herbicide tolerance, deposited asATCC PTA-6708, described in US-A 2006-282915 or WO 2006/130436); EventMS11 (oilseed rape, pollination control—herbicide tolerance, depositedas ATCC PTA-850 or PTA-2485, described in WO 01/031042); Event MS8(oilseed rape, pollination control—herbicide tolerance, deposited asATCC PTA-730, described in WO 01/041558 or US-A 2003-188347); EventNK603 (corn, herbicide tolerance, deposited as ATCC PTA-2478, describedin US-A 2007-292854); Event PE-7 (rice, insect control, not deposited,described in WO 2008/114282); Event RF3 (oilseed rape, pollinationcontrol—herbicide tolerance, deposited as ATCC PTA-730, described in WO01/041558 or US-A 2003-188347); Event RT73 (oilseed rape, herbicidetolerance, not deposited, described in WO 02/036831 or US-A2008-070260); Event T227-1 (sugar beet, herbicide tolerance, notdeposited, described in WO 02/44407 or US-A 2009-265817); Event T25(corn, herbicide tolerance, not deposited, described in US-A 2001-029014or WO 01/051654); Event T304-40 (cotton, insect control—herbicidetolerance, deposited as ATCC PTA-8171, described in US-A 2010-077501 orWO 2008/122406); Event T342-142 (cotton, insect control, not deposited,described in WO 2006/128568); Event TC1507 (corn, insectcontrol—herbicide tolerance, not deposited, described in US-A2005-039226 or WO 2004/099447); Event VIP1034 (corn, insectcontrol—herbicide tolerance, deposited as ATCC PTA-3925., described inWO 03/052073), Event 32316 (corn, insect control-herbicide tolerance,deposited as PTA-11507, described in WO 2011/084632), Event 4114 (corn,insect control-herbicide tolerance, deposited as PTA-11506, described inWO 2011/084621).

Among the diseases of plants or crops that can be controlled by themethod according to the invention, mention can be made of:

Powdery mildew diseases such as:

-   -   Blumeria diseases, caused for example by Blumeria graminis;    -   Podosphaera diseases, caused for example by Podosphaera        leucotricha;    -   Sphaerotheca diseases, caused for example by Sphaerotheca        fuliginea;    -   Uncinula diseases, caused for example by Uncinula necator;

Rust diseases such as:

-   -   Gymnosporangium diseases, caused for example by Gymnosporangium        sabinae;    -   Hemileia diseases, caused for example by Hemileia vastatrix;    -   Phakopsora diseases, caused for example by Phakopsora pachyrhizi        or Phakopsora meibomiae;    -   Puccinia diseases, caused for example by Puccinia recondite,        Puccinia graminis or Puccinia striiformis;

Uromyces diseases, caused for example by Uromyces appendiculatus;

Oomycete diseases such as:

-   -   Albugo diseases caused for example by Albugo candida;    -   Bremia diseases, caused for example by Bremia lactucae;    -   Peronospora diseases, caused for example by Peronospora pisi        or P. brassicae;    -   Phytophthora diseases, caused for example by Phytophthora        infestans;    -   Plasmopara diseases, caused for example by Plasmopara viticola;    -   Pseudoperonospora diseases, caused for example by        Pseudoperonospora humuli or Pseudoperonospora cubensis;    -   Pythium diseases, caused for example by Pythium ultimum;

Leafspot, leaf blotch and leaf blight diseases such as:

-   -   Alternaria diseases, caused for example by Alternaria solani;    -   Cercospora diseases, caused for example by Cercospora beticola;    -   Cladiosporum diseases, caused for example by Cladiosporium        cucumerinum;    -   Cochliobolus diseases, caused for example by Cochliobolus        sativus (Conidiaform: Drechslera, Syn: Helminthosporium) or        Cochliobolus miyabeanus;    -   Colletotrichum diseases, caused for example by Colletotrichum        lindemuthanium;    -   Cycloconium diseases, caused for example by Cycloconium        oleaginum;    -   Diaporthe diseases, caused for example by Diaporthe citri;    -   Elsinoe diseases, caused for example by Elsinoe fawcettii;    -   Gloeosporium diseases, caused for example by Gloeosporium        laeticolor;    -   Glomerella diseases, caused for example by Glomerella cingulata;    -   Guignardia diseases, caused for example by Guignardia bidwelli;    -   Leptosphaeria diseases, caused for example by Leptosphaeria        maculans; Leptosphaeria nodorum;    -   Magnaporthe diseases, caused for example by Magnaporthe grisea;    -   Mycosphaerella diseases, caused for example by Mycosphaerella        graminicola; Mycosphaerella arachidicola; Mycosphaerella        fijiensis;    -   Phaeosphaeria diseases, caused for example by Phaeosphaeria        nodorum;    -   Pyrenophora diseases, caused for example by Pyrenophora teres,        or Pyrenophora tritici repentis;    -   Ramularia diseases, caused for example by Ramularia collocygni,        or Ramularia areola;    -   Rhynchosporium diseases, caused for example by Rhynchosporium        secalis;    -   Septoria diseases, caused for example by Septoria apii or        Septoria lycopercisi;    -   Typhula diseases, caused for example by Typhula incamata;    -   Venturia diseases, caused for example by Venturia inaequalis;

Root, Sheath and stem diseases such as:

-   -   Corticium diseases, caused for example by Corticium graminearum;    -   Fusarium diseases, caused for example by Fusarium oxysporum;    -   Gaeumannomyces diseases, caused for example by Gaeumannomyces        graminis;    -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;    -   Sarocladium diseases caused for example by Sarocladium oryzae;    -   Sclerotium diseases caused for example by Sclerotium oryzae;    -   Tapesia diseases, caused for example by Tapesia acuformis;    -   Thielaviopsis diseases, caused for example by Thielaviopsis        basicola;

Ear and panicle diseases such as:

-   -   Alternaria diseases, caused for example by Alternaria spp.;    -   Aspergillus diseases, caused for example by Aspergillus flavus;    -   Cladosporium diseases, caused for example by Cladosporium spp.;    -   Claviceps diseases, caused for example by Claviceps purpurea;    -   Fusarium diseases, caused for example by Fusarium culmorum;    -   Gibberella diseases, caused for example by Gibberella zeae;    -   Monographella diseases, caused for example by Monographella        nivalis;

Smut and bunt diseases such as:

-   -   Sphacelotheca diseases, caused for example by Sphacelotheca        reiliana;    -   Tilletia diseases, caused for example by Tilletia caries;    -   Urocystis diseases, caused for example by Urocystis occulta;    -   Ustilago diseases, caused for example by Ustilago nuda;

Fruit rot and mould diseases such as:

-   -   Aspergillus diseases, caused for example by Aspergillus flavus;    -   Botrytis diseases, caused for example by Botrytis cinerea;    -   Penicillium diseases, caused for example by Penicillium        expansum;    -   Rhizopus diseases caused by example by Rhizopus stolonifer    -   Sclerotinia diseases, caused for example by Sclerotinia        sclerotiorum;    -   Verticilium diseases, caused for example by Verticilium        alboatrum;

Seed and soil borne decay, mould, wilt, rot and damping-off diseases:

-   -   Alternaria diseases, caused for example by Alternaria        brassicicola;    -   Aphanomyces diseases, caused for example by Aphanomyces        euteiches;    -   Ascochyta diseases, caused for example by Ascochyta lentis;    -   Aspergillus diseases, caused for example by Aspergillus flavus;    -   Cladosporium diseases, caused for example by Cladosporium        herbarum;    -   Cochliobolus diseases, caused for example by Cochliobolus        sativus;    -   (Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium);    -   Colletotrichum diseases, caused for example by Colletotrichum        coccodes;    -   Fusarium diseases, caused for example by Fusarium culmorum;    -   Gibberella diseases, caused for example by Gibberella zeae;    -   Macrophomina diseases, caused for example by Macrophomina        phaseolina;    -   Monographella diseases, caused for example by Monographella        nivalis;    -   Penicillium diseases, caused for example by Penicillium        expansum;    -   Phoma diseases, caused for example by Phoma lingam;    -   Phomopsis diseases, caused for example by Phomopsis sojae;    -   Phytophthora diseases, caused for example by Phytophthora        cactorum;    -   Pyrenophora diseases, caused for example by Pyrenophora        graminea;    -   Pyricularia diseases, caused for example by Pyricularia oryzae;    -   Pythium diseases, caused for example by Pythium ultimum;    -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;    -   Rhizopus diseases, caused for example by Rhizopus oryzae;    -   Sclerotium diseases, caused for example by Sclerotium rolfsii;    -   Septoria diseases, caused for example by Septoria nodorum;    -   Typhula diseases, caused for example by Typhula incarnate;    -   Verticillium diseases, caused for example by Verticillium        dahliae;

Canker, broom and dieback diseases such as:

-   -   Nectria diseases, caused for example by Nectria galligena;

Blight diseases such as:

-   -   Monilinia diseases, caused for example by Monilinia laxa;

Leaf blister or leaf curl diseases such as:

-   -   Exobasidium diseases caused for example by Exobasidium vexans;    -   Taphrina diseases, caused for example by Taphrina deformans;

Decline diseases of wooden plants such as:

-   -   Esca diseases, caused for example by Phaemoniella clamydospora;    -   Eutypa dyeback, caused for example by Eutypa lata;    -   Ganoderma diseases caused for example by Ganoderma boninense;    -   Rigidoporus diseases caused for example by Rigidoporus lignosus;

Diseases of Flowers and Seeds such as:

-   -   Botrytis diseases caused for example by Botrytis cinerea;

Diseases of Tubers such as:

-   -   Rhizoctonia diseases caused for example by Rhizoctonia solani;    -   Helminthosporium diseases caused for example by Helminthosporium        solani;

Club root diseases such as:

-   -   Plasmodiophora diseases, cause for example by Plamodiophora        brassicae;

Diseases caused by Bacterial Organisms such as:

-   -   Xanthomonas species for example Xanthomonas campestris pv.        oryzae;    -   Pseudomonas species for example Pseudomonas syringae pv.        lachrymans;    -   Erwinia species for example Erwinia amylovora.

The composition according to the invention may also be used againstfungal diseases liable to grow on or inside timber. The term “timber”means all types of species of wood, and all types of working of thiswood intended for construction, for example solid wood, high-densitywood, laminated wood, and plywood. The method for treating timberaccording to the invention mainly consists in contacting one or morecompounds according to the invention or a composition according to theinvention; this includes for example direct application, spraying,dipping, injection or any other suitable means.

The dose of active compound usually applied in the method of treatmentaccording to the invention is generally and advantageously from 10 to800 g/ha, preferably from 50 to 300 g/ha for applications in foliartreatment. The dose of active substance applied is generally andadvantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to150 g per 100 kg of seed in the case of seed treatment.

It is clearly understood that the doses indicated herein are given asillustrative examples of the method according to the invention. A personskilled in the art will know how to adapt the application doses, notablyaccording to the nature of the plant or crop to be treated.

The compounds or mixtures according to the invention can also be usedfor the preparation of composition useful to curatively or preventivelytreat human or animal fungal diseases such as, for example, mycoses,dermatoses, trichophyton diseases and candidiases or diseases caused byAspergillus spp., for example Aspergillus fumigatus.

The present invention further relates to the use of compounds of theformula (I) as herein defined for the control of phytopathogenic fungi.

The present invention further relates to the use of compounds of theformula (I) as herein defined for the treatment of transgenic plants.

The present invention further relates to the use of compounds of theformula (I) as herein defined for the treatment of seed and of seed oftransgenic plants.

The present invention further relates to a process for producingcompositions for controlling phytopathogenic harmful fungi,characterized in that derivatives of the formula (I) as herein definedare mixed with extenders and/or surfactants.

The various aspects of the invention will now be illustrated withreference to the following table of compound examples and the followingpreparation or efficacy examples.

Table 1 illustrates in a non-limiting manner examples of compounds offormula (I) according to the invention:

wherein A can be selected in the list consisting of the followinggroups: A-G1, A-G2, A-G3, A-G4, A-G5, A-G6, A-G7 and A-G8:

wherein * denotes the point of attachment the group A to the(thio)carbonyl moiety.

In table 1, unless otherwise specified, M+H (Apcl+) means the molecularion peak plus 1 a.m.u. (atomic mass unit) as observed in massspectroscopy via positive atmospheric pressure chemical ionisation.

In table 1, the logP values were determined in accordance with EECDirective 79/831 Annex V.A8 by HPLC (High Performance LiquidChromatography) on a reversed-phase column (C 18), using the methoddescribed below:

Temperature: 40° C.; Mobile phases: 0.1% aqueous formic acid andacetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (comprising 3to 16 carbon atoms) with known logP values (determination of the logPvalues by the retention times using linear interpolation between twosuccessive alkanones). Lambda-max-values were determined usingUV-spectra from 200 nm to 400 nm and the peak values of thechromatographic signals.

In table 1, “position” denotes the point of attachment of thecycloalkenyl ring to the phenyl ring.

TABLE 1 Example A T Z¹ Z² Z³ (X)_(n) position

M + H logP NMR I.1 A-G1 O cyclopropyl Me H — 2- cyclopenten-1-yl 3683.78 + 3.80⁽¹⁾ I.2 A-G2 O cyclopropyl H H — 2- cyclopent-1-en-1-yl 3723.63 table 3 I.3 A-G3 O cyclopropyl H H — 2- cyclopent-1-en-1-yl 3904.06 table 3 I.4 A-G4 O cyclopropyl H H — 2- cyclopent-1-en-1-yl 4064.26 table 3 I.5 A-G5 O cyclopropyl H H — 2- cyclopent-1-en-1-yl 3714.13 table 3 I.6 A-G6 O cyclopropyl H H — 2- cyclopent-1-en-1-yl 4504.85 table 3 I.7 A-G3 O cyclopropyl H H 2-CF3-6-F 5- cyclopent-1-en-1-yl476 4.81 table 3 I.8 A-G4 O cyclopropyl H H 2-Cl 5- cyclopent-1-en-1-yl440 4.82 table 3 I.9 A-G3 O cyclopropyl H H 2-Cl 5- cyclopent-1-en-1-yl424 4.59 table 3 I.10 A-G2 O cyclopropyl H H 2-Cl 5- cyclopent-1-en-1-yl406 4.14 table 3 I.11 A-G5 O cyclopropyl H H 2-Cl 5- cyclopent-1-en-1-yl405 4.63 table 3 I.12 A-G6 O cyclopropyl H H 2-Cl 5- cyclopent-1-en-1-yl484 5.51 table 3 I.13 A-G7 O cyclopropyl H H 2-Cl 2- cyclopent-1-en-1-yl423 4.82 table 3 I.14 A-G8 O cyclopropyl H H 2-Cl 2- cyclopent-1-en-1-yl370 5.36 I.15 A-G3 O cyclopropyl H H 4-Cl 2- cyclopenten-1-yl 424 4.49 +4.67⁽¹⁾ I.16 A-G3 O cyclopropyl H H 4-F 2- cyclopenten-1-yl 408 3.94 +4.01⁽¹⁾ I.17 A-G3 O cyclopropyl H H 4-Me 2- cyclopenten-1-yl 404 4.21 +4.29 + 4.44⁽¹⁾ I.18 A-G3 O cyclopropyl H H 5-(cyclopent- 2-cyclopent-1-en-1-yl 456 5.62 table 3 1-en-1-yl) I.19 A-G3 O cyclopropylH H 5,6-diF 2- cyclopent-1-en-1-yl 426 4.11 table 3 I.20 A-G3 Ocyclopropyl H H 5-Cl 2- cyclopent-1-en-1-yl 424 4.54 table 3 I.21 A-G6 Ocyclopropyl H H 5-Cl 2- cyclopent-1-en-1-yl 484 5.36 I.22 A-G2 Ocyclopropyl H H 5-Cl 2- cyclopent-1-en-1-yl 406 4.06 table 3 I.23 A-G4 Ocyclopropyl H H 5-Cl 2- cyclopent-1-en-1-yl 440 4.74 table 3 I.24 A-G5 Ocyclopropyl H H 5-Cl 2- cyclopent-1-en-1-yl 405 4.58 table 3 I.25 A-G3 Ocyclopropyl Me H 5-F 2- cyclopent-1-en-1-yl 422 4.34 table 3 I.26 A-G3 Ocyclopropyl H H 5-Me 2- cyclopenten-1-yl 404 4.24 + 4.31⁽¹⁾ I.27 A-G2 Ocyclopropyl H H — 2- cyclohex-1-en-1-yl 386 3.99 table 3 I.28 A-G3 Ocyclopropyl H H — 2- cyclohex-1-en-1-yl 404 4.49 table 3 I.29 A-G4 Ocyclopropyl H H — 2- cyclohex-1-en-1-yl 420 4.66 table 3 I.30 A-G5 Ocyclopropyl H H — 2- cyclohex-1-en-1-yl 385 4.46 table 3 I.31 A-G6 Ocyclopropyl H H — 2- cyclohex-1-en-1-yl 464 5.22 table 3 I.32 A-G3 Ocyclopropyl Me H — 2- cyclohex-1-en-1-yl 418 4.61 table 3 I.33 A-G3 Ocyclopropyl H H 2-Cl 5- cyclohex-1-en-1-yl 438 4.92 table 3 I.34 A-G4 Ocyclopropyl H H 2-Cl 5- cyclohex-1-en-1-yl 454 5.14 table 3 I.35 A-G6 Ocyclopropyl H H 2-Cl 5- cyclohex-1-en-1-yl 498 5.87 table 3 I.36 A-G5 Ocyclopropyl H H 2-Cl 5- cyclohex-1-en-1-yl 419 4.93 table 3 I.37 A-G2 Ocyclopropyl H H 2-Cl 5- cyclohex-1-en-1-yl 420 4.46 table 3 I.38 A-G4 Ocyclopropyl H H 5-Cl 2- cyclohex-1-en-1-yl 454 5.11 table 3 I.39 A-G2 Ocyclopropyl H H 5-Cl 2- cyclohex-1-en-1-yl 420 4.44 table 3 I.40 A-G5 Ocyclopropyl H H 5-Cl 2- cyclohex-1-en-1-yl 419 4.93 table 3 I.41 A-G3 Ocyclopropyl H H 5-Cl 2- cyclohex-1-en-1-yl 438 4.88 table 3 I.42 A-G6 Ocyclopropyl H H 5-Cl 2- cyclohex-1-en-1-yl 498 5.78 table 3 I.43 A-G3 Scyclopropyl H H 5-Cl 2- cyclohex-1-en-1-yl 454 5.56 table 3 I.44 A-G4 Ocyclopropyl H H 5-F 2- cyclohex-1-en-1-yl 438 4.69 table 3 I.45 A-G3 Ocyclopropyl Me H — 2- 4-methyl 432 5.03 table 3 cyclohex-1-en-1-yl I.46A-G3 O cyclopropyl H H 5-Cl 2- 4-methyl 452 5.36 table 3cyclohex-1-en-1-yl I.47 A-G4 O cyclopropyl H H 5-F 2- 4-methyl 452 5.14table 3 cyclohex-1-en-1-yl I.48 A-G4 O cyclopropyl H H 5-F 2- 4-methyl468 5.77 table 3 2- cyclohex-1-en-1-yl I.49 A-G2 O cyclopropyl H H — 2-cyclohept-1-en-1-yl 400 4.44 table 3 I.50 A-G5 O cyclopropyl H H — 2-cyclohept-1-en-1-yl 399 4.93 table 3 I.51 A-G4 O cyclopropyl H H — 2-cyclohept-1-en-1-yl 434 5.06 table 3 I.52 A-G6 O cyclopropyl H H — 2-cyclohept-1-en-1-yl 478 5.78 table 3 I.53 A-G3 O cyclopropyl H H — 2-cyclohept-1-en-1-yl 418 4.85 table 3 I.54 A-G3 O cyclopropyl H H 5-Cl 2-cyclohept-1-en-1-yl 452 5.31 table 3 I.55 A-G5 O cyclopropyl H H 5-Cl 2-cyclohept-1-en-1-yl 433 5.34 table 3 I.56 A-G4 O cyclopropyl H H 5-Cl 2-cyclohept-1-en-1-yl 468 5.54 table 3 I.57 A-G2 O cyclopropyl H H 5-Cl 2-cyclohept-1-en-1-yl 434 4.87 table 3 I.58 A-G6 O cyclopropyl H H 5-Cl 2-cyclohept-1-en-1-yl 512 6.27 table 3 I.59 A-G3 O rel-(1R,2R)-2methyl H H5-Me 2- cyclopent-1-en-1-yl 418 4.85 table 3 cyclopropyl I.60 A-G3 Orel-(1R,2R)-2methyl H H 5-Me 2- cyclohex-1-en-1-yl 432 5.22 table 3cyclopropyl Note ⁽¹⁾: mixture of 2 or more isomers

Table 2 illustrates in a non limiting manner examples of compounds offormula (IIa) according to the invention

In table 2, M+H (Apcl+) and logP are defined as for table 1.

In table 2, “position” denotes the point of attachment of thecycloalkenyl ring to the phenyl ring.

TABLE 2 Example Z² Z³ (X)_(n) position

M + H logP IIa.1 Me H — 2- cyclopent-1-en-1-yl 228 1.72 IIa.2 H H — 2-cyclopent-1-en-1-yl 1.19 IIa.3 H H 5-Cl 2- cyclopent-1-en-1-yl 1.28IIa.4 Me H 5-F 2- cyclopent-1-en-1-yl 246 1.56 IIa.5 H H 2-Cl 5-cyclopent-1-en-1-yl 1.39 IIa.6 H H — 2- cyclohex-1-en-1-yl 1.37 IIa.7 HH 5-Cl 2- cyclohex-1-en-1-yl 1.45 IIa.8 H H 2-Cl 5- cyclohex-1-en-1-yl1.45 IIa.9 H H — 2- cyclohept-1-en-1-yl 1.45 IIa.10 H H 5-Cl 2-cyclohept-1-en-1-yl 1.71

Table 3 provides the NMR data (′H) of a selected number of compoundsfrom table 1.

The ¹H-NMR data of selected examples are stated in the form of ¹H-NMRpeak lists. For each signal peak, the δ value in ppm and the signalintensity in brackets are listed.

Intensity of sharp signals correlates with the height of the signals ina printed example of a NMR spectrum in cm and shows the real relationsof signal intensities. From broad signals several peaks or the middle ofthe signal and their relative intensity in comparison to the mostintensive signal in the spectrum can be shown.

The ¹H-NMR peak lists are similar to classical ¹H-NMR prints and containtherefore usually all peaks, which are listed at classicalNMR-interpretation. Additionally they can show like classical ¹H-NMRprints signals of solvents, stereoisomers of the target compounds, whichare also object of the invention, and/or peaks of impurities. To showcompound signals in the delta-range of solvents and/or water the usualpeaks of solvents, for example peaks of DMSO in DMSO-d6 and the peak ofwater are shown in our ¹H-NMR peak lists and have usually on average ahigh intensity.

The peaks of stereoisomers of the target compounds and/or peaks ofimpurities have usually on average a lower intensity than the peaks oftarget compounds (for example with a purity >90%). Such stereoisomersand/or impurities can be typical for the specific preparation process.Therefore their peaks can help to recognize the reproduction of ourpreparation process via “side-products-fingerprints”.

An expert, who calculates the peaks of the target compounds with knownmethods (MestreC, ACD-simulation, but also with empirically evaluatedexpectation values), can isolate the peaks of the target compounds asneeded optionally using additional intensity filters. This isolationwould be similar to relevant peak picking at classical ¹H-NMRinterpretation.

Further details of NMR-data description with peak lists can be found inthe publication “Citation of NMR Peaklist Data within PatentApplications” of the Research Disclosure Database Number 564025.

TABLE 3 NMR peak lists Frequency Example Solvent (Mhz) ¹H-NMR I.2 CDCl3300 7.9096 (0.49); 7.6314 (0.95); 7.6083 (0.85); 7.3098 (1.39); 7.2624(29.49); 7.2534 (1.58); 7.2504 (1.62); 7.2431 (1.78); 7.2184 (37.46);7.1901 (1.47); 7.1840 (1.35); 7.1274 (2.57); 6.9450 (1.29); 5.6692(4.27); 5.2997 (12.19); 4.7905 (7.63); 4.6514 (0.56); 4.6333 (0.55);3.9525 (16.00); 3.9185 (2.11); 2.6695 (3.88); 2.6460 (6.75); 2.6282(4.55); 2.5579 (0.34); 2.5384 (1.43); 2.5307 (3.08); 2.5227 (3.16);2.5145 (3.50); 2.5069 (5.35); 2.4995 (5.21); 2.4905 (3.44); 2.4814(3.94); 2.4735 (3.49); 2.4657 (1.45); 2.0348 (2.08); 2.0261 (0.82);2.0091 (6.19); 1.9848 (8.04); 1.9702 (1.42); 1.9597 (5.14); 1.9356(1.64); 1.5947 (17.24); 1.2553 (0.49); 1.2404 (0.85); 0.7041 (0.55);0.6665 (4.38); 0.6437 (8.02); 0.6387 (8.31); 0.6298 (9.25); 0.5883(0.80); 0.0106 (0.62); −0.0002 (19.69); −0.0111 (0.83) I.3 CDCl3 3007.2616 (44.11); 7.2411 (9.91); 7.2290 (18.51); 7.2214 (6.80); 7.2143(6.75); 7.2010 (2.86); 7.1888 (1.23); 7.1790 (0.62); 7.0677 (0.95);6.9104 (0.41); 6.8851 (1.85); 6.7034 (0.89); 5.6885 (2.57); 5.3004(1.43); 4.7972 (4.81); 3.8139 (16.00); 2.9574 (1.50); 2.8843 (1.28);2.6839 (3.60); 2.6670 (4.61); 2.6438 (2.75); 2.5590 (1.05); 2.5509(2.39); 2.5428 (2.48); 2.5348 (2.74); 2.5271 (4.18); 2.5198 (4.11);2.5107 (2.75); 2.5017 (3.20); 2.4938 (2.89); 2.4859 (1.18); 2.0552(1.65); 2.0458 (0.47); 2.0296 (4.97); 2.0052 (6.45); 1.9905 (1.15);1.9799 (4.20); 1.9558 (1.26); 1.5686 (29.31); 1.2552 (0.42); 0.5609(8.35); 0.0107 (0.81); −0.0002 (29.69); −0.0110 (1.41) I.4 CDCl3 5007.3481 (3.27); 7.2584 (41.16); 7.2481 (2.98); 7.2330 (9.08); 7.2255(7.50); 7.2178 (12.25); 7.2016 (8.23); 7.0869 (0.52); 6.8671 (0.95);6.7573 (1.95); 6.6469 (1.04); 5.7624 (0.49); 5.6994 (2.99); 5.2942(12.96); 4.8477 (3.36); 4.6709 (1.11); 4.6602 (1.09); 4.5626 (0.37);3.8976 (16.00); 2.7128 (4.40); 2.6997 (4.47); 2.6743 (5.40); 2.5497(8.89); 2.0549 (2.10); 2.0405 (6.28); 2.0258 (8.68); 2.0110 (6.20);1.9961 (2.23); 1.5585 (65.45); 1.2578 (0.81); 0.7827 (0.37); 0.7461(0.32); 0.6592 (0.55); 0.6354 (0.55); 0.5182 (5.65); 0.4692 (4.56);−0.0002 (28.00) I.5 CDCl3 300 7.3604 (1.52); 7.2605 (9.72); 7.2488(0.63); 7.2364 (1.51); 7.2283 (2.83); 7.2218 (3.55); 7.2105 (10.58);7.1979 (4.56); 7.1908 (1.66); 7.1698 (3.25); 6.9793 (1.62); 6.9199(1.45); 6.8768 (2.77); 6.8709 (2.45); 5.6863 (1.89); 5.6794 (2.75);5.6725 (1.88); 5.6655 (0.67); 5.2977 (6.06); 4.8052 (11.48); 3.6631(16.00); 2.6937 (0.78); 2.6847 (1.53); 2.6779 (2.22); 2.6698 (1.89);2.6591 (3.80); 2.6535 (3.10); 2.6459 (2.20); 2.6431 (2.17); 2.6360(2.28); 2.6282 (1.68); 2.6220 (1.14); 2.5408 (0.59); 2.5329 (1.30);2.5249 (1.35); 2.5170 (1.50); 2.5092 (2.29); 2.5017 (2.22); 2.4925(1.48); 2.4837 (1.74); 2.4758 (1.55); 2.4679 (0.62); 2.0342 (0.91);2.0086 (2.69); 1.9844 (3.48); 1.9699 (0.60); 1.9590 (2.26); 1.9350(0.68); 1.5993 (5.65); 0.6529 (3.49); 0.6404 (4.77); 0.6288 (8.10);−0.0002 (5.75) I.6 CDCl3 300 7.4444 (1.40); 7.4311 (1.74); 7.4243(1.76); 7.4126 (1.88); 7.3270 (0.45); 7.3212 (0.44); 7.3067 (0.47);7.2922 (0.55); 7.2774 (0.91); 7.2759 (0.88); 7.2744 (0.85); 7.2608(15.72); 7.2560 (3.30); 7.2545 (3.27); 7.2534 (3.17); 7.2461 (5.16);7.2397 (2.97); 7.2242 (7.65); 7.1816 (1.09); 7.1630 (0.73); 6.9363(1.30); 6.9198 (1.33); 5.7194 (1.54); 5.2969 (16.00); 5.2909 (0.67);5.2894 (0.50); 5.2878 (0.42); 5.2864 (0.35); 4.8634 (3.93); 4.6978(0.36); 4.6800 (0.35); 4.4865 (0.38); 2.6906 (2.24); 2.5388 (4.51);2.5210 (3.25); 2.0661 (0.77); 2.0421 (2.31); 2.0177 (3.19); 1.9937(2.27); 1.6181 (1.69); 0.8808 (0.32); 0.8015 (0.49); 0.4300 (3.57);−0.0002 (8.53); −0.0111 (0.38) I.7 DMSO- 400 7.6228 (1.75); 7.6017(8.33); 7.5813 (2.13); 7.5605 (0.81); 7.1134 (2.09); 6.9788 d6 (4.79);6.8443 (2.41); 6.5075 (2.45); 6.5026 (2.47); 5.7632 (10.01); 4.8758(7.14); 3.7887 (16.00); 3.7374 (0.41); 3.3777 (0.33); 3.3279 (27.08);3.2780 (0.34); 2.7665 (1.53); 2.7494 (2.69); 2.7339 (1.79); 2.7293(1.66); 2.5865 (1.37); 2.5806 (1.51); 2.5641 (2.88); 2.5500 (1.99);2.5436 (1.86); 2.5326 (1.23); 2.5277 (1.42); 2.5190 (10.46); 2.5145(21.30); 2.5100 (29.19); 2.5054 (21.44); 2.5009 (10.96); 2.4694 (0.87);2.4647 (0.90); 2.4601 (0.94); 2.4555 (0.83); 2.4202 (0.86); 2.3370(0.35); 1.9944 (1.00); 1.9751 (2.83); 1.9565 (3.75); 1.9376 (2.67);1.9190 (0.95); 1.2755 (0.55); 1.2060 (1.86); 0.6222 (0.49); 0.5973(2.99); 0.5907 (2.87); 0.5804 (3.93); 0.5749 (4.20); 0.5635 (4.93);0.5351 (0.79) I.8 DMSO- 400 7.9529 (2.17); 7.4297 (15.17); 7.4047(0.74); 7.3496 (8.91); 7.3284 (0.58); 7.1712 d6 (1.47); 7.0362 (2.99);6.9013 (1.52); 6.2925 (5.19); 4.7231 (1.91); 4.6335 (0.41); 3.9348(0.46); 3.8974 (16.00); 3.6015 (0.43); 3.3356 (285.02); 3.2622 (0.38);2.8909 (14.12); 2.7604 (1.52); 2.7497 (1.50); 2.7316 (13.32); 2.6760(0.64); 2.6719 (0.78); 2.6672 (0.68); 2.6438 (3.19); 2.6265 (5.44);2.6109 (3.49); 2.6065 (3.19); 2.5069 (73.82); 2.5028 (93.15); 2.4985(71.02); 2.4747 (4.49); 2.4688 (3.83); 2.3338 (0.64); 2.3295 (0.77);2.0021 (1.88); 1.9832 (5.23); 1.9646 (6.74); 1.9461 (4.68); 1.9274(1.42); 1.2342 (0.58); 1.0695 (1.06); 0.5522 (7.01); −0.0002 (2.68) I.9CDCl3 400 7.3140 (6.03); 7.2957 (12.36); 7.2733 (0.64); 7.2699 (0.78);7.2602 (25.00); 7.0056 (1.36); 6.8691 (2.83); 6.7324 (1.42); 6.1849(0.96); 6.1791 (2.53); 6.1741 (3.80); 6.1692 (2.47); 6.1633 (0.88);4.8000 (4.04); 3.8173 (16.00); 2.7683 (0.67); 2.6842 (0.79); 2.6786(1.87); 2.6734 (2.08); 2.6673 (1.84); 2.6598 (3.10); 2.6553 (3.34);2.6410 (2.26); 2.6357 (2.15); 2.6304 (0.98); 2.5485 (0.77); 2.5425(1.83); 2.5363 (1.88); 2.5301 (2.05); 2.5241 (3.11); 2.5186 (3.03);2.5122 (2.09); 2.5054 (2.30); 2.4992 (2.09); 2.4933 (0.80); 2.0520(1.36); 2.0431 (0.46); 2.0328 (3.75); 2.0243 (0.74); 2.0143 (4.88);2.0045 (0.74); 1.9952 (3.26); 1.9770 (1.03); 1.5555 (16.00); 0.8819(0.38); 0.6543 (6.68); 0.0079 (0.56); −0.0002 (16.79); −0.0084 (0.63)I.10 DMSO- 400 8.4239 (1.70); 7.9601 (1.32); 7.4491 (0.35); 7.4217(9.23); 7.4191 (9.08); 7.3012 d6 (1.44); 7.2818 (3.56); 7.1653 (3.08);7.0294 (1.48); 6.2920 (1.63); 6.2873 (2.46); 6.2828 (1.66); 4.7008(8.61); 3.9373 (16.00); 3.3389 (114.15); 2.8979 (10.41); 2.8681 (0.66);2.7387 (8.23); 2.6787 (0.32); 2.6267 (1.04); 2.6218 (1.20); 2.6039(2.03); 2.5894 (1.29); 2.5843 (1.19); 2.5319 (0.88); 2.5185 (17.94);2.5141 (35.84); 2.5096 (47.23); 2.5050 (35.08); 2.5006 (17.67); 2.4872(2.41); 2.4686 (1.49); 2.4625 (1.29); 2.3364 (0.33); 1.9922 (0.76);1.9730 (2.06); 1.9546 (2.62); 1.9360 (1.80); 1.9171 (0.56); 0.7627(0.68); 0.7446 (2.74); 0.7315 (2.77); 0.7274 (2.43); 0.7146 (0.87);0.6157 (1.05); 0.6045 (2.77); 0.5977 (2.97); 0.5899 (2.30); 0.5763(0.67) I.11 DMSO- 400 7.9593 (1.09); 7.4912 (2.32); 7.4047 (8.43);7.2547 (4.25); 7.1138 (4.54); 6.9697 d6 (1.24); 6.2641 (2.23); 4.6861(7.86); 3.6933 (16.00); 3.3381 (94.35); 2.8973 (7.87); 2.7379 (6.32);2.6085 (1.20); 2.5912 (2.04); 2.5760 (1.28); 2.5712 (1.21); 2.5133(33.63); 2.5091 (44.25); 2.5051 (35.01); 2.4771 (2.26); 2.4611 (1.41);2.4554 (1.24); 2.3357 (0.32); 1.9846 (0.72); 1.9657 (1.98); 1.9471(2.50); 1.9284 (1.71); 1.9096 (0.51); 0.7682 (0.69); 0.7509 (2.76);0.7371 (2.71); 0.7207 (0.82); 0.6013 (1.03); 0.5899 (2.76); 0.5835(2.98); 0.5623 (0.66) I.12 DMSO- 400 7.9605 (2.15); 7.7852 (3.69);7.7721 (3.81); 7.4388 (10.96); 7.3812 (9.28); 7.0896 d6 (2.09); 6.3378(5.95); 4.7253 (4.93); 3.3389 (169.80); 2.8980 (16.00); 2.7551 (1.36);2.7392 (14.67); 2.7387 (14.68); 2.6880 (3.52); 2.6832 (4.11); 2.6654(6.09); 2.6504 (3.91); 2.6455 (3.59); 2.5188 (31.14); 2.5144 (59.44);2.5099 (77.59); 2.5053 (58.59); 2.5009 (31.71); 2.4851 (4.57); 2.4791(3.89); 2.3412 (0.47); 2.3366 (0.61); 2.3323 (0.48); 2.0115 (1.95);1.9923 (5.56); 1.9738 (7.31); 1.9552 (4.99); 1.9363 (1.53); 1.2405(0.55); 0.7616 (0.45); 0.4741 (6.80) I.13 CDCl3 300 7.3147 (16.98);7.2615 (16.74); 7.1259 (1.11); 6.9445 (2.27); 6.7629 (1.15); 6.1986(1.48); 6.1919 (2.15); 6.1855 (1.41); 4.8100 (4.82); 2.7665 (16.00);2.6975 (1.04); 2.6906 (1.18); 2.6825 (1.08); 2.6723 (1.84); 2.6663(2.23); 2.6476 (2.14); 2.6407 (1.66); 2.6300 (1.62); 2.6214 (0.69);2.6128 (0.80); 2.5933 (0.41); 2.5616 (1.01); 2.5531 (1.09); 2.5453(1.27); 2.5375 (1.81); 2.5303 (1.75); 2.5125 (1.36); 2.5041 (1.19);2.4965 (0.49); 2.0761 (0.73); 2.0505 (2.06); 2.0259 (2.64); 2.0089(2.66); 2.0009 (1.79); 1.9762 (0.53); 1.5568 (5.09); 0.7153 (4.04);0.6994 (7.57); −0.0002 (7.85); −0.0110 (0.37) I.18 DMSO- 400 7.3632(2.89); 7.3588 (3.06); 7.3431 (3.54); 7.3387 (3.75); 7.3141 (0.37);7.3053 d6 (0.35); 7.2686 (5.92); 7.2650 (5.39); 7.2470 (0.71); 7.2423(0.74); 7.1950 (1.09); 7.1875 (1.35); 7.1751 (4.89); 7.1548 (3.62);7.1227 (3.20); 6.9880 (6.99); 6.8533 (3.44); 6.2956 (3.24); 6.2910(4.55); 5.7653 (12.73); 5.7368 (2.87); 5.7157 (0.57); 4.7319 (0.46);4.6681 (6.99); 3.8042 (16.00); 3.7555 (0.46); 3.6696 (1.04); 3.3903(3.08); 3.3404 (281.94); 3.2905 (2.80); 2.6712 (4.63); 2.6653 (4.97);2.6506 (7.83); 2.6332 (6.14); 2.5668 (0.76); 2.5624 (1.28); 2.5579(1.66); 2.5534 (1.18); 2.5487 (0.67); 2.5303 (2.40); 2.5256 (3.95);2.5168 (50.41); 2.5124 (105.43); 2.5079 (144.12); 2.5034 (105.11);2.4989 (52.07); 2.4839 (9.71); 2.4678 (6.48); 2.4630 (6.35); 2.4061(0.51); 2.3872 (0.42); 2.3559 (0.35); 2.3393 (0.88); 2.3347 (1.10);2.3302 (0.89); 2.2302 (0.33); 2.2253 (0.33); 2.2166 (0.37); 2.2040(0.34); 2.1960 (0.40); 2.1914 (0.40); 2.1714 (0.37); 2.0987 (0.46);2.0790 (0.48); 2.0652 (0.35); 2.0461 (0.42); 2.0220 (0.38); 1.9919(3.01); 1.9729 (7.72); 1.9547 (10.03); 1.9362 (7.09); 1.9174 (2.27);1.8070 (0.33); 1.7810 (0.48); 1.7718 (0.41); 1.7589 (0.45); 1.7469(0.42); 1.7336 (0.33); 1.7240 (0.41); 1.6834 (0.43); 1.6627 (0.47);1.6533 (0.47); 1.6427 (0.36); 1.6318 (0.46); 1.4107 (0.35); 0.5937(4.23); 0.5799 (4.22); 0.5354 (0.77); 0.5251 (0.87); 0.4842 (5.32);0.4776 (5.60) I.19 DMSO- 400 7.3945 (1.01); 7.3732 (2.12); 7.3518(1.51); 7.3478 (1.94); 7.3265 (1.03); 7.1055 d6 (1.51); 7.1014 (1.79);7.0963 (2.83); 7.0890 (1.63); 7.0841 (1.34); 7.0799 (1.30); 7.0709(1.18); 7.0675 (1.10); 6.9618 (5.11); 6.8272 (2.57); 5.7619 (8.97);5.7447 (2.82); 4.7911 (8.55); 4.0455 (0.35); 4.0276 (0.34); 3.7856(16.00); 3.3873 (2.93); 3.3373 (211.41); 3.3135 (0.64); 3.2874 (2.46);2.6507 (1.36); 2.6459 (1.55); 2.6320 (2.68); 2.6279 (2.74); 2.6140(1.72); 2.6091 (1.57); 2.5642 (0.34); 2.5596 (0.46); 2.5320 (0.57);2.5187 (12.57); 2.5142 (26.09); 2.5097 (35.63); 2.5051 (25.27); 2.5007(11.73); 2.4641 (1.72); 2.4595 (1.91); 2.4427 (2.71); 2.4274 (1.82);2.4219 (1.63); 2.3731 (0.94); 2.3413 (0.49); 2.3367 (0.49); 2.3319(0.39); 1.9958 (1.60); 1.9636 (0.82); 1.9447 (2.39); 1.9263 (3.21);1.9079 (2.18); 1.8893 (0.69); 1.2060 (0.69); 1.1999 (0.50); 1.1821(0.89); 1.1643 (0.45); 0.8651 (0.37); 0.5892 (0.61); 0.5704 (2.91);0.5576 (2.82); 0.5531 (2.70); 0.5415 (1.46); 0.5285 (0.58); 0.5220(0.52); 0.5020 (1.39); 0.4916 (3.63); 0.4825 (3.42); 0.4629 (0.72) I.20DMSO- 400 7.9529 (0.98); 7.3288 (2.57); 7.3234 (2.73); 7.3082 (4.97);7.3028 (5.36); 7.2661 d6 (8.68); 7.2455 (4.47); 7.1924 (5.85); 7.1878(5.51); 7.1173 (2.83); 6.9825 (6.22); 6.8477 (3.08); 5.7951 (3.24);4.6765 (10.25); 4.6469 (0.47); 3.8062 (16.00); 3.3336 (212.64); 3.2995(0.42); 2.8909 (6.95); 2.7310 (5.99); 2.6808 (1.80); 2.6762 (1.87);2.6717 (1.86); 2.6671 (1.69); 2.6321 (4.08); 2.5113 (33.51); 2.5070(63.96); 2.5025 (81.93); 2.4980 (60.54); 2.4937 (31.66); 2.4705 (3.36);2.4647 (2.89); 2.3337 (0.45); 2.3293 (0.57); 2.3248 (0.45); 1.9822(1.49); 1.9632 (4.30); 1.9448 (5.71); 1.9261 (3.86); 1.9077 (1.20);1.7212 (0.41); 1.6074 (0.40); 1.4367 (0.83); 1.2339 (0.53); 1.0692(1.41); 0.6151 (4.38); 0.6015 (4.44); 0.5867 (1.62); 0.5632 (0.38);0.5420 (0.41); 0.5313 (0.35); 0.5003 (1.90); 0.4898 (5.12); 0.4830(5.49); 0.4624 (1.19); −0.0002 (3.64) I.22 DMSO- 400 8.3938 (1.44);7.9527 (0.96); 7.3136 (1.61); 7.3077 (2.40); 7.2931 (2.74); 7.2877 d6(3.09); 7.2604 (0.34); 7.2477 (5.62); 7.2271 (3.05); 7.1802 (3.89);7.1748 (4.05); 7.1700 (3.60); 7.0338 (1.48); 5.7737 (2.69); 4.6784(8.91); 3.9916 (0.60); 3.9309 (16.00); 3.8996 (0.40); 3.3369 (162.17);2.8909 (6.88); 2.8218 (0.99); 2.7319 (5.81); 2.6716 (0.34); 2.6465(1.26); 2.6418 (1.45); 2.6277 (2.44); 2.6237 (2.51); 2.6098 (1.60);2.6048 (1.47); 2.5248 (0.81); 2.5114 (17.75); 2.5072 (35.03); 2.5027(45.68); 2.4982 (33.30); 2.4940 (16.39); 2.4622 (1.37); 2.4566 (1.45);2.4402 (2.43); 2.4255 (1.67); 2.4198 (1.51); 2.3295 (0.34); 1.9432(0.86); 1.9241 (2.37); 1.9058 (3.11); 1.8872 (2.14); 1.8685 (0.69);1.2342 (0.34); 1.0694 (1.26); 0.7176 (0.70); 0.6999 (3.02); 0.6866(3.10); 0.6828 (2.66); 0.6696 (0.93); 0.5432 (1.15); 0.5321 (3.16);0.5258 (3.36); 0.5172 (2.67); 0.5040 (0.75); −0.0002 (1.79) I.23 DMSO-400 7.9526 (1.46); 7.3185 (2.55); 7.2979 (6.06); 7.2722 (7.24); 7.1802(1.61); 7.0456 d6 (2.87); 6.9108 (1.43); 5.8252 (3.64); 4.7024 (4.75);4.4825 (0.37); 3.9338 (0.78); 3.9050 (16.00); 3.8602 (0.68); 3.8370(0.45); 3.8234 (0.42); 3.8169 (0.42); 3.8058 (0.40); 3.3737 (0.72);3.3342 (310.27); 2.8908 (10.42); 2.7315 (10.95); 2.6713 (3.34); 2.6666(3.49); 2.6533 (4.34); 2.5112 (43.13); 2.5069 (78.26); 2.5025 (99.71);2.4980 (73.55); 2.3337 (0.53); 2.3291 (0.66); 2.3246 (0.50); 2.0059(1.27); 1.9885 (3.52); 1.9702 (4.79); 1.9523 (3.49); 1.8910 (0.39);1.2340 (0.71); 1.1651 (0.33); 1.0693 (1.92); 0.5187 (4.37); 0.5031(4.43); 0.4486 (5.15); −0.0002 (3.92) I.24 DMSO- 400 7.9590 (0.75);7.4756 (2.37); 7.3034 (1.19); 7.2980 (1.29); 7.2827 (2.55); 7.2775 d6(2.89); 7.2686 (1.47); 7.2492 (4.69); 7.2286 (2.12); 7.1443 (3.49);7.1392 (3.55); 7.1249 (4.10); 7.1203 (3.30); 6.9820 (1.32); 5.7900(2.00); 5.7854 (2.70); 4.6750 (7.87); 3.6944 (16.00); 3.3375 (83.54);2.8969 (5.07); 2.8640 (0.98); 2.8561 (1.22); 2.8476 (0.96); 2.7375(4.51); 2.6533 (1.51); 2.6394 (2.43); 2.6355 (2.51); 2.6215 (1.56);2.6165 (1.40); 2.5130 (30.93); 2.5087 (39.19); 2.5043 (30.40); 2.4847(1.77); 2.4679 (2.46); 2.4531 (1.63); 2.4477 (1.40); 1.9647 (0.76);1.9457 (2.19); 1.9272 (2.86); 1.9086 (1.91); 1.8901 (0.57); 0.7334(0.73); 0.7160 (2.96); 0.7029 (2.93); 0.6859 (0.84); 0.5401 (1.10);0.5287 (3.01); 0.5226 (3.29); 0.5144 (2.68); 0.5012 (0.73) I.25 DMSO-300 11.8449 (0.35); 7.4134 (2.17); 7.4045 (2.13); 7.3773 (2.23); 7.3684(2.14); 7.2316 d6 (1.66); 7.2109 (1.98); 7.2032 (3.35); 7.1825 (3.17);7.1495 (2.00); 7.1405 (2.51); 7.1290 (3.03); 7.1217 (3.15); 7.1130(3.21); 7.0938 (1.14); 7.0846 (1.01); 6.9811 (0.33); 6.9493 (5.08);6.7695 (2.65); 5.7761 (0.37); 5.7603 (0.55); 5.7359 (0.32); 5.6380(3.54); 5.5920 (1.90); 5.5696 (1.98); 5.5504 (0.58); 3.7730 (16.00);3.5331 (0.33); 3.4654 (0.33); 3.3318 (497.44); 3.2668 (1.44); 3.2477(0.78); 3.2229 (0.49); 2.7274 (0.45); 2.6487 (0.59); 2.6216 (0.90);2.6009 (1.18); 2.5715 (0.71); 2.5139 (28.30); 2.5080 (61.16); 2.5019(84.36); 2.4958 (62.90); 2.4899 (31.30); 2.3756 (3.30); 2.3663 (2.71);2.2998 (1.70); 2.2778 (1.28); 2.1858 (0.42); 2.1714 (0.35); 1.9337(0.80); 1.9083 (3.10); 1.8843 (4.27); 1.8594 (2.63); 1.8363 (0.72);1.5973 (1.55); 1.5740 (1.63); 1.5449 (9.19); 1.5216 (9.25); 1.4233(0.33); 0.6881 (1.10); 0.6686 (1.06); 0.6534 (1.00); 0.5251 (0.85);0.5005 (1.63); 0.4940 (1.99); 0.4829 (2.10); 0.4706 (2.24); 0.4387(1.19); 0.1376 (1.06); 0.1166 (1.21); 0.1005 (1.26); 0.0439 (0.41);0.0108 (1.15); −0.0002 (43.07); −0.0110 (2.03) I.27 CDCl3 300 7.6405(0.44); 7.6092 (0.37); 7.3178 (0.48); 7.2631 (17.84); 7.2511 (0.37);7.2377 (1.23); 7.2239 (2.56); 7.2154 (4.79); 7.2061 (12.19); 7.1965(2.65); 7.1886 (0.84); 7.1322 (1.30); 7.1213 (2.34); 7.1165 (1.67);7.1065 (2.25); 7.0987 (1.12); 7.0945 (1.33); 7.0895 (1.30); 6.9515(0.47); 5.5551 (1.47); 5.3006 (16.00); 4.7530 (3.01); 3.9535 (7.05);2.6313 (0.88); 2.1991 (2.11); 2.1573 (0.88); 2.1372 (2.08); 2.1287(2.52); 2.1171 (2.68); 2.1093 (2.05); 1.7827 (0.50); 1.7638 (1.34);1.7521 (1.97); 1.7461 (2.03); 1.7327 (2.21); 1.7268 (2.07); 1.7127(1.19); 1.7056 (1.17); 1.6899 (1.17); 1.6838 (1.26); 1.6702 (2.17);1.6641 (2.21); 1.6522 (2.04); 1.6448 (1.98); 1.6348 (1.32); 1.6158(0.56); 1.6143 (0.56); 1.6129 (0.57); 1.6114 (0.57); 1.6099 (0.59);1.5992 (25.62); 0.6757 (2.14); 0.6506 (4.65); 0.6421 (4.63); −0.0002(9.45); −0.0111 (0.38) I.28 CDCl3 300 7.2624 (8.47); 7.2289 (14.22);7.2186 (10.67); 7.1983 (1.99); 7.1217 (2.55); 7.1166 (2.10); 7.1076(2.57); 7.0982 (2.15); 7.0901 (1.70); 7.0815 (1.10); 6.8959 (1.57);6.7137 (0.80); 5.5755 (2.12); 5.2978 (16.00); 4.7563 (4.37); 3.8112(14.73); 2.6854 (1.44); 2.6781 (1.50); 2.2175 (3.31); 2.1811 (1.61);2.1606 (3.20); 2.1519 (3.82); 2.1407 (4.01); 2.1331 (3.05); 1.8015(0.76); 1.7825 (2.03); 1.7712 (3.00); 1.7655 (3.05); 1.7520 (3.28);1.7460 (3.10); 1.7324 (1.79); 1.7250 (1.78); 1.7098 (1.80); 1.7040(1.91); 1.6905 (3.26); 1.6844 (3.24); 1.6722 (3.09); 1.6651 (2.90);1.6544 (1.94); 1.6350 (0.72); 1.6158 (3.20); 0.5725 (7.83); −0.0002(5.78) I.29 CDCl3 300 7.3344 (0.85); 7.2621 (8.77); 7.2574 (1.00);7.2559 (1.01); 7.2384 (2.20); 7.2316 (3.36); 7.2203 (2.44); 7.2082(3.13); 7.1859 (0.58); 7.1780 (0.43); 7.1188 (1.00); 7.1048 (0.92);7.0915 (0.81); 6.9566 (0.39); 6.7736 (0.76); 6.5913 (0.39); 5.5910(0.98); 5.2983 (16.00); 4.8103 (0.99); 3.9030 (4.98); 2.7206 (0.76);2.7112 (0.68); 2.2311 (1.42); 2.2077 (1.59); 2.1750 (2.03); 1.7844(1.33); 1.7654 (1.50); 1.7367 (1.23); 1.7137 (1.71); 1.6967 (1.61);1.6053 (1.59); 0.5256 (1.89); 0.4896 (1.49); −0.0002 (5.86) I.30 CDCl3300 7.3661 (1.45); 7.2607 (11.53); 7.2531 (0.35); 7.2472 (0.32); 7.2206(1.79); 7.2121 (9.61); 7.2011 (6.20); 7.1960 (3.73); 7.1810 (2.43);7.1755 (3.64); 7.1211 (0.63); 7.1114 (1.88); 7.1070 (1.80); 7.0967(2.08); 7.0891 (1.12); 7.0844 (1.04); 7.0796 (1.06); 6.9847 (1.55);6.9208 (1.40); 6.8767 (2.71); 6.8708 (2.44); 5.5757 (1.02); 5.5693(1.47); 5.5634 (2.06); 5.5577 (1.51); 5.5512 (1.09); 5.2978 (10.64);4.7684 (11.00); 3.6628 (16.00); 2.6786 (0.37); 2.6604 (0.94); 2.6425(1.55); 2.6346 (0.73); 2.6247 (0.92); 2.6060 (0.45); 2.2135 (2.26);2.2071 (2.34); 2.1875 (1.38); 2.1649 (0.66); 2.1447 (1.80); 2.1360(2.20); 2.1245 (2.36); 2.1166 (1.79); 2.1050 (1.03); 1.7845 (0.45);1.7654 (1.18); 1.7544 (1.73); 1.7482 (1.77); 1.7350 (1.95); 1.7288(1.81); 1.7150 (1.06); 1.7081 (1.04); 1.6924 (1.05); 1.6866 (1.12);1.6730 (1.90); 1.6668 (1.96); 1.6548 (1.80); 1.6473 (1.76); 1.6369(1.17); 1.6177 (0.47); 1.5997 (11.38); 0.6577 (4.47); 0.6538 (5.01);0.6378 (12.20); −0.0002 (6.55) I.31 DMSO- 500 7.7355 (2.01); 7.3911(1.78); 7.2605 (2.01); 7.2459 (5.18); 7.2338 (5.41); 7.2310 d6 (5.80);7.2174 (3.26); 7.2045 (1.67); 7.0997 (2.04); 7.0929 (2.14); 7.0757(1.45); 7.0584 (2.21); 5.7413 (16.00); 5.5674 (1.95); 4.6720 (4.54);3.2899 (31.63); 2.6179 (1.67); 2.5020 (3.45); 2.4985 (4.75); 2.4949(3.55); 2.4918 (1.84); 2.2098 (3.18); 2.1399 (4.31); 2.0681 (0.40);1.7295 (3.44); 1.6827 (0.92); 1.6403 (4.44); 1.5907 (0.39); 0.6890(0.33); 0.3879 (4.70); −0.0002 (0.68) I.32 DMSO- 400 7.6238 (2.14);7.6177 (2.08); 7.6051 (1.73); 7.6011 (2.44); 7.3179 (0.63); 7.3129 d6(0.91); 7.2995 (2.85); 7.2940 (3.35); 7.2926 (3.39); 7.2844 (5.36);7.2755 (3.90); 7.2699 (2.90); 7.2562 (0.96); 7.2515 (0.57); 7.1039(2.22); 7.0962 (0.43); 7.0864 (3.08); 7.0820 (2.06); 7.0781 (1.71);7.0704 (2.33); 7.0640 (2.44); 6.9688 (4.47); 6.8339 (2.47); 5.7660(2.25); 5.6588 (0.69); 5.6411 (2.47); 5.6233 (2.51); 5.6057 (0.68);5.4697 (2.48); 3.8620 (0.43); 3.7738 (16.00); 3.3373 (47.71); 2.6766(0.35); 2.5300 (0.86); 2.5252 (1.45); 2.5166 (19.94); 2.5121 (41.54);2.5076 (56.37); 2.5031 (39.78); 2.4987 (1.34); 2.1411 (2.29); 2.1358(2.25); 2.0859 (0.47); 2.0718 2.1798 (1.52); 2.1694 (1.34); 2.1411(2.29); 2.1358 (2.25); 2.0859 (0.47); 2.0718 (0.63); 2.0634 (0.56);2.0275 (1.00); 2.0193 (1.03); 1.9604 (0.97); 1.9519 (1.01); 1.9221(0.39); 1.9158 (0.46); 1.9077 (0.48); 1.6977 (0.62); 1.6818 (1.15);1.6656 (1.85); 1.6501 (1.99); 1.6350 (1.47); 1.6200 (0.78); 1.6028(0.53); 1.5822 (1.09); 1.5670 (2.39); 1.5529 (2.93); 1.5318 (10.86);1.5140 (10.06); 0.7603 (1.11); 0.7450 (0.96); 0.7344 (0.96); 0.5241(0.48); 0.5176 (0.88); 0.5003 (3.22); 0.4847 (3.22); 0.4673 (0.87);0.4609 (0.46); 0.1345 (0.45); 0.1242 (1.07); 0.1101 (1.09); 0.0986(1.20); 0.0940 (1.12); 0.0881 (0.95); 0.0838 (0.88) I.33 CDCl3 4007.3024 (3.55); 7.2815 (10.84); 7.2771 (5.50); 7.2621 (9.56); 7.2427(4.42); 7.2370 (3.19); 7.2220 (2.05); 7.2164 (1.78); 7.0037 (1.28);6.8672 (2.65); 6.7306 (1.34); 6.1170 (0.99); 6.1132 (1.78); 6.1074(2.27); 6.1031 (3.41); 6.0989 (2.19); 6.0931 (1.68); 6.0892 (0.87);5.2964 (8.08); 4.7955 (3.80); 3.8109 (16.00); 2.7567 (0.69); 2.3619(1.87); 2.3569 (2.16); 2.3467 (3.79); 2.3421 (3.86); 2.3366 (2.62);2.3314 (2.26); 2.3268 (2.07); 2.3211 (0.98); 2.2195 (0.80); 2.2132(1.49); 2.2038 (2.88); 2.1977 (3.56); 2.1942 (2.80); 2.1880 (3.66);2.1821 (2.73); 2.1727 (1.58); 2.1666 (0.71); 1.7956 (1.09); 1.7875(1.02); 1.7806 (2.77); 1.7725 (2.50); 1.7665 (3.98); 1.7577 (2.56);1.7516 (3.77); 1.7424 (1.11); 1.7364 (1.48); 1.6754 (1.60); 1.6695(1.21); 1.6604 (4.15); 1.6543 (2.65); 1.6455 (3.97); 1.6395 (2.44);1.6315 (2.57); 1.6243 (0.96); 1.6163 (0.91); 1.5971 (2.30); 0.6562(6.10); −0.0002 (6.07) I.34 DMSO- 400 7.9531 (1.80); 7.4177 (2.49);7.3973 (4.36); 7.3727 (0.68); 7.3603 (5.26); 7.3551 d6 (6.64); 7.3350(14.50); 7.1608 (1.48); 7.0257 (3.02); 6.8910 (1.54); 6.1633 (4.23);4.7163 (1.59); 4.6299 (0.44); 3.8971 (16.00); 3.3328 (215.48); 3.2954(0.48); 2.8909 (12.15); 2.7484 (1.63); 2.7319 (11.41); 2.6761 (0.57);2.6715 (0.66); 2.6673 (0.49); 2.5069 (76.65); 2.5025 (94.58); 2.4980(67.58); 2.3284 (6.94); 2.3242 (6.86); 2.1822 (4.72); 2.1767 (5.80);2.1675 (5.86); 1.7450 (1.55); 1.7302 (4.10); 1.7216 (4.51); 1.7162(5.84); 1.7072 (4.50); 1.7015 (5.40); 1.6917 (1.99); 1.6865 (2.09);1.6599 (0.34); 1.6247 (2.31); 1.6190 (2.17); 1.6100 (5.96); 1.6041(4.61); 1.5953 (6.09); 1.5894 (4.29); 1.5814 (4.01); 1.5669 (1.40);1.2339 (0.59); 0.5500 (6.35); −0.0002 (7.14) I.35 DMSO- 400 7.9530(2.21); 7.7757 (2.77); 7.7630 (2.84); 7.4414 (0.42); 7.4145 (1.45);7.3945 d6 (3.00); 7.3679 (8.25); 7.3477 (2.63); 7.3144 (0.33); 7.0691(1.63); 6.2208 (2.20); 6.2111 (4.39); 6.2012 (2.26); 4.7148 (3.80);3.3278 (86.31); 3.0604 (0.34); 2.8904 (16.00); 2.7482 (0.56); 2.7311(14.11); 2.7162 (1.35); 2.6810 (0.68); 2.6760 (0.71); 2.6714 (0.74);2.6668 (0.59); 2.5111 (23.40); 2.5067 (46.53); 2.5022 (61.24); 2.4976(45.27); 2.4933 (22.67); 2.3888 (0.35); 2.3552 (5.12); 2.3508 (5.26);2.3355 (2.98); 2.1913 (3.62); 2.1857 (4.54); 2.1764 (4.64); 2.1710(3.67); 1.7505 (1.22); 1.7356 (3.21); 1.7272 (3.47); 1.7216 (4.58);1.7127 (3.54); 1.7068 (4.26); 1.6978 (1.61); 1.6918 (1.70); 1.6254(1.80); 1.6195 (1.70); 1.6105 (4.59); 1.6046 (3.70); 1.5957 (4.75);1.5899 (3.48); 1.5817 (3.17); 1.5668 (1.10); 1.4464 (0.37); 1.2331(0.68); 0.7420 (0.40); 0.4633 (5.42) I.36 DMSO- 400 7.9527 (0.90);7.4725 (2.11); 7.3903 (2.27); 7.3694 (4.94); 7.3389 (2.19); 7.3334 d6(2.32); 7.3180 (0.97); 7.3125 (1.16); 7.2469 (1.25); 7.2309 (2.94);7.2257 (2.69); 7.1129 (2.52); 7.1079 (2.72); 7.1041 (3.75); 6.9604(1.32); 6.1628 (0.95); 6.1566 (1.29); 6.1529 (1.94); 6.1429 (0.95);4.6785 (7.37); 3.6824 (16.00); 3.3262 (41.09); 2.8901 (7.23); 2.8651(0.84); 2.7310 (5.93); 2.5236 (0.68); 2.5105 (13.80); 2.5061 (27.54);2.5016 (36.39); 2.4971 (26.74); 2.4927 (13.27); 2.2941 (2.12); 2.2896(2.20); 2.2745 (1.16); 2.1647 (1.55); 2.1588 (1.95); 2.1495 (2.01);2.1437 (1.54); 2.1348 (0.90); 1.7246 (0.52); 1.7097 (1.40); 1.7014(1.46); 1.6955 (2.01); 1.6867 (1.49); 1.6808 (1.90); 1.6714 (0.65);1.6656 (0.72); 1.6058 (0.78); 1.6002 (0.71); 1.5909 (2.04); 1.5851(1.58); 1.5762 (2.04); 1.5703 (1.46); 1.5622 (1.34); 1.5471 (0.45);0.7591 (0.56); 0.7415 (2.39); 0.7283 (2.48); 0.7241 (2.13); 0.7114(0.76); 0.5958 (0.88); 0.5849 (2.44); 0.5783 (2.64); 0.5699 (2.12);0.5566 (0.63) I.37 DMSO- 400 8.4079 (1.75); 7.9531 (1.20); 7.4037(2.47); 7.3828 (5.72); 7.3559 (2.61); 7.3505 d6 (2.76); 7.3349 (1.10);7.3294 (1.33); 7.2918 (1.40); 7.2606 (3.44); 7.2555 (3.08); 7.1558(3.19); 7.0199 (1.54); 6.1750 (1.11); 6.1652 (2.28); 6.1554 (1.12);4.6917 (8.63); 3.9261 (16.00); 3.3243 (25.17); 2.8906 (9.21); 2.8379(0.68); 2.7315 (7.67); 2.5241 (0.89); 2.5108 (17.25); 2.5064 (34.03);2.5019 (44.50); 2.4974 (32.49); 2.4930 (15.98); 2.3330 (0.34); 2.3049(2.50); 2.3004 (2.59); 2.2853 (1.37); 2.1725 (1.82); 2.1665 (2.30);2.1572 (2.36); 2.1516 (1.81); 1.7315 (0.61); 1.7165 (1.64); 1.7083(1.74); 1.7024 (2.35); 1.6937 (1.77); 1.6877 (2.21); 1.6787 (0.76);1.6728 (0.84); 1.6116 (0.90); 1.6060 (0.83); 1.5968 (2.37); 1.5909(1.84); 1.5821 (2.40); 1.5761 (1.70); 1.5680 (1.57); 1.5530 (0.53);0.7522 (0.63); 0.7345 (2.75); 0.7211 (2.84); 0.7170 (2.45); 0.7044(0.89); 0.6095 (1.04); 0.5986 (2.85); 0.5917 (3.06); 0.5840 (2.35);0.5701 (0.69) I.38 DMSO- 400 7.9530 (2.19); 7.3328 (0.35); 7.3267(0.38); 7.2933 (3.11); 7.2729 (4.55); 7.2574 d6 (4.16); 7.1775 (1.46);7.1553 (3.59); 7.1352 (2.87); 7.1176 (0.68); 7.1035 (0.47); 7.0430(2.42); 6.9084 (1.16); 5.5776 (2.77); 4.6533 (3.18); 4.4308 (0.33);4.4178 (0.45); 4.4039 (0.38); 3.9025 (13.26); 3.8115 (0.40); 3.3360(271.03); 2.8910 (16.00); 2.7317 (13.37); 2.7042 (1.88); 2.6942 (2.55);2.6717 (1.37); 2.5114 (35.98); 2.5072 (69.04); 2.5027 (88.84); 2.4982(64.95); 2.4939 (32.51); 2.3338 (0.55); 2.3293 (0.69); 2.3247 (0.54);2.1487 (4.78); 1.7354 (3.50); 1.7245 (3.59); 1.6530 (3.87); 1.6418(4.07); 1.2341 (0.74); 1.1951 (0.32); 1.1652 (0.32); 0.5191 (3.56);0.5037 (3.85); 0.4557 (4.39); −0.0002 (3.96) I.39 DMSO- 400 8.3871(1.71); 7.9594 (0.50); 7.3215 (1.33); 7.3019 (1.84); 7.2963 (2.02);7.2815 d6 (2.30); 7.2759 (2.57); 7.2000 (3.90); 7.1947 (3.62); 7.1856(3.08); 7.1367 (4.80); 7.1163 (3.81); 7.0495 (1.41); 5.5638 (2.08);4.6406 (8.39); 3.9303 (16.00); 3.3351 (76.93); 2.8972 (3.68); 2.7673(1.08); 2.7379 (3.36); 2.5172 (18.22); 2.5131 (34.56); 2.5086 (44.49);2.5041 (32.56); 2.4999 (16.36); 2.1643 (2.54); 2.0565 (2.38); 2.0485(2.41); 1.7026 (0.58); 1.6884 (1.49); 1.6750 (2.17); 1.6654 (1.95);1.6609 (2.05); 1.6458 (0.84); 1.5914 (0.95); 1.5820 (2.10); 1.5773(1.97); 1.5676 (2.13); 1.5541 (1.40); 0.7228 (0.69); 0.7048 (2.97);0.6917 (3.09); 0.6877 (2.64); 0.6748 (0.94); 0.5648 (1.06); 0.5540(3.09); 0.5474 (3.32); 0.5390 (2.62); 0.5258 (0.75) I.40 DMSO- 4007.4600 (2.10); 7.2834 (2.08); 7.2787 (2.31); 7.2635 (1.99); 7.2578(2.15); 7.1512 d6 (3.45); 7.1458 (3.28); 7.1374 (2.92); 7.1291 (4.39);7.1154 (2.62); 7.1088 (4.82); 6.9941 (1.30); 5.5598 (1.92); 4.6329(7.32); 3.6886 (16.00); 3.3371 (70.49); 2.8984 (1.32); 2.8160 (0.64);2.8074 (0.78); 2.7988 (1.04); 2.7899 (0.79); 2.7824 (0.58); 2.7388(1.12); 2.5189 (14.49); 2.5146 (28.45); 2.5100 (37.18); 2.5055 (27.04);2.5011 (13.14); 2.1683 (2.12); 2.0855 (1.92); 2.0776 (1.94); 1.7189(0.46); 1.7050 (1.21); 1.6913 (1.76); 1.6819 (1.58); 1.6772 (1.65);1.6666 (0.74); 1.6131 (0.80); 1.6028 (1.72); 1.5982 (1.62); 1.5886(1.73); 1.5753 (1.10); 0.7321 (0.58); 0.7143 (2.47); 0.7012 (2.58);0.6971 (2.16); 0.6842 (0.75); 0.5518 (0.86); 0.5406 (2.53); 0.5340(2.70); 0.5255 (2.20); 0.5125 (0.61) I.41 DMSO- 400 7.3047 (3.22);7.2991 (3.38); 7.2843 (3.82); 7.2787 (4.18); 7.1913 (4.39); 7.1459 d6(8.06); 7.1254 (6.49); 7.1178 (2.89); 6.9830 (6.33); 6.8483 (3.14);5.5581 (2.65); 4.6461 (0.85); 4.6249 (9.37); 3.8016 (16.00); 3.3068(35.36); 2.6740 (0.79); 2.6694 (1.08); 2.6648 (1.15); 2.6422 (1.46);2.5506 (0.42); 2.5229 (1.63); 2.5095 (34.71); 2.5051 (70.17); 2.5005(94.63); 2.4960 (66.47); 2.4916 (30.81); 2.4513 (0.35); 2.3320 (0.46);2.3274 (0.61); 2.3229 (0.45); 2.1640 (3.48); 2.1099 (3.65); 2.1020(3.72); 1.7353 (0.81); 1.7212 (2.22); 1.7079 (3.33); 1.6983 (3.03);1.6937 (3.08); 1.6587 (0.33); 1.6343 (1.55); 1.6244 (3.22); 1.6197(3.12); 1.6101 (3.27); 1.5966 (2.10); 1.2969 (0.32); 1.2791 (0.68);1.2477 (3.24); 0.8752 (1.48); 0.8585 (4.93); 0.8408 (1.89); 0.6402(0.87); 0.6223 (3.75); 0.6090 (3.78); 0.5933 (1.36); 0.5536 (0.46);0.5141 (1.49); 0.5031 (4.43); 0.4956 (4.73); 0.4752 (1.02); 0.0079(0.33); −0.0002 (9.35); −0.0085 (0.34) I.42 DMSO- 400 7.9600 (2.15);7.7784 (2.71); 7.7661 (2.91); 7.3902 (3.74); 7.3025 (2.70); 7.2837 d6(3.49); 7.1565 (2.98); 7.1366 (2.53); 7.0642 (2.88); 7.0523 (2.84);5.6082 (2.77); 4.6536 (7.40); 4.3808 (0.35); 3.3373 (172.57); 2.8978(16.00); 2.7551 (0.38); 2.7386 (13.48); 2.7239 (0.38); 2.6784 (2.38);2.6737 (2.38); 2.5183 (29.94); 2.5140 (58.30); 2.5095 (75.81); 2.5049(55.67); 2.5006 (27.66); 2.3408 (0.40); 2.3361 (0.51); 2.3318 (0.38);2.2038 (4.12); 2.1421 (4.82); 1.9160 (0.38); 1.7336 (3.81); 1.7248(3.81); 1.6461 (4.57); 1.6363 (4.69); 1.2417 (0.52); 0.8158 (0.35);0.7003 (0.39); 0.3949 (9.71) I.43 CDCl3 400 7.2599 (28.03); 7.2135(8.13); 7.1971 (3.57); 7.1916 (2.43); 7.1864 (2.68); 7.0805 (4.54);7.0747 (1.39); 7.0640 (1.24); 7.0584 (3.82); 7.0491 (4.80); 7.0287(0.33); 6.9119 (2.29); 5.6145 (1.47); 5.6098 (2.06); 5.6056 (2.77);5.6018 (2.15); 5.4179 (0.39); 5.2979 (2.32); 3.8107 (16.00); 3.6991(1.18); 2.9096 (0.63); 2.9042 (0.96); 2.8924 (1.43); 2.8815 (1.00);2.8759 (1.01); 2.2177 (2.84); 2.2125 (3.17); 2.1982 (3.29); 2.1903(3.00); 2.1837 (2.86); 2.1751 (3.10); 2.1686 (2.47); 2.0455 (0.36);1.8082 (0.57); 1.7938 (1.68); 1.7801 (2.76); 1.7704 (2.34); 1.7659(2.63); 1.7551 (1.36); 1.7507 (1.31); 1.7157 (1.37); 1.7051 (2.74);1.7006 (2.53); 1.6907 (2.89); 1.6773 (1.89); 1.5394 (7.50); 0.8137(0.39); 0.8069 (0.39); 0.7293 (0.63); 0.7108 (2.94); 0.6993 (3.88);0.6882 (1.47); 0.6811 (0.88); 0.6652 (1.73); 0.6518 (3.57); 0.6336(3.38); 0.6211 (0.64); 0.6149 (0.56); 0.0080 (0.62); −0.0002 (19.78);−0.0084 (0.68) I.44 DMSO- 400 7.1761 (1.18); 7.1543 (1.64); 7.1392(1.34); 7.0836 (1.29); 7.0772 (1.46); 7.0623 d6 (2.16); 7.0559 (2.57);7.0463 (1.72); 7.0354 (1.25); 6.9899 (1.30); 6.9659 (1.38); 6.9124(0.73); 5.7601 (16.00); 5.5694 (1.54); 4.6596 (2.93); 3.9051 (7.42);3.3136 (20.48); 2.7528 (0.60); 2.7426 (1.31); 2.7350 (1.58); 2.7250(2.48); 2.7153 (1.54); 2.7081 (1.31); 2.6978 (0.67); 2.6812 (0.37);2.6767 (0.54); 2.6720 (0.37); 2.5300 (1.28); 2.5166 (30.32); 2.5121(61.95); 2.5076 (83.77); 2.5031 (59.21); 2.4987 (27.71); 2.4625 (0.38);2.4581 (0.40); 2.3390 (0.41); 2.3345 (0.54); 2.3299 (0.39); 2.1583(2.89); 2.0795 (0.33); 1.7418 (2.11); 1.7319 (2.10); 1.6488 (2.39);0.5227 (2.15); 0.5098 (2.22); 0.4552 (2.64) I.45 DMSO- 400 7.6241(1.16); 7.6188 (2.33); 7.6127 (1.62); 7.6012 (2.13); 7.5963 (1.78);7.3135 d6 (0.73); 7.3088 (0.97); 7.2952 (2.79); 7.2902 (3.29); 7.2881(2.99); 7.2798 (5.45); 7.2719 (3.71); 7.2654 (2.90); 7.2517 (0.94);7.2471 (0.68); 7.0987 (2.26); 7.0843 (2.16); 7.0801 (2.69); 7.0761(2.13); 7.0729 (1.35); 7.0682 (1.79); 7.0625 (2.31); 7.0581 (1.46);6.9637 (4.60); 6.8288 (2.51); 5.7662 (4.07); 5.6365 (0.47); 5.6189(1.70); 5.6102 (1.39); 5.6011 (1.82); 5.5925 (1.34); 5.5837 (0.63);5.5748 (0.41); 5.4347 (2.06); 3.8630 (0.39); 3.7758 (16.00); 3.3375(49.19); 2.6769 (0.34); 2.5304 (0.90); 2.5256 (1.49); 2.5169 (18.61);2.5125 (39.55); 2.5079 (54.93); 2.5034 (40.75); 2.4990 (20.78); 2.3348(0.43); 2.3303 (0.39); 2.2778 (0.60); 2.2610 (0.64); 2.2064 (1.76);2.1995 (1.76); 2.1718 (0.62); 2.1383 (1.26); 2.1141 (1.07); 2.0641(0.52); 2.0531 (0.52); 2.0267 (0.58); 1.7230 (1.06); 1.6869 (2.02);1.6608 (1.65); 1.6126 (0.69); 1.5647 (0.46); 1.5311 (10.32); 1.5133(10.38); 1.3526 (0.42); 1.3406 (0.46); 1.3230 (0.58); 1.3096 (0.60);1.2959 (0.62); 1.2822 (0.68); 1.2643 (0.58); 1.2513 (0.59); 1.2393(0.46); 0.9413 (7.95); 0.9279 (7.29); 0.8638 (0.32); 0.7560 (0.72);0.7299 (1.11); 0.7076 (0.61); 0.5239 (0.73); 0.5085 (2.16); 0.4963(2.98); 0.4833 (1.89); 0.4789 (1.66); 0.1355 (0.71); 0.1254 (0.77);0.1117 (0.96); 0.1070 (1.03); 0.1016 (1.17); 0.0881 (0.58); 0.0770(0.61); 0.0711 (0.56) I.46 DMSO- 400 7.3007 (3.06); 7.2951 (3.35);7.2803 (3.94); 7.2747 (4.38); 7.1797 (4.70); 7.1752 d6 (4.48); 7.1463(8.07); 7.1258 (6.45); 7.1160 (3.02); 7.0506 (0.33); 6.9812 (6.17);6.8464 (3.09); 5.7531 (3.79); 5.5242 (2.48); 4.6604 (0.76); 4.6210(5.01); 4.6104 (5.14); 4.5714 (0.84); 3.8017 (16.00); 3.3072 (20.51);2.6696 (1.42); 2.6649 (1.51); 2.6602 (1.55); 2.6544 (1.56); 2.5231(1.33); 2.5098 (21.58); 2.5053 (44.06); 2.5008 (60.48); 2.4963 (44.46);2.4918 (22.73); 2.3322 (0.68); 2.3277 (0.84); 2.3230 (0.80); 2.2855(1.05); 2.2482 (1.18); 2.2319 (1.28); 2.1887 (1.49); 2.1614 (1.93);2.1182 (0.98); 1.7809 (1.89); 1.7507 (3.34); 1.7443 (3.20); 1.7213(3.21); 1.3987 (0.42); 1.3847 (0.63); 1.3684 (0.99); 1.3595 (1.21);1.3416 (1.16); 1.3291 (1.02); 1.3162 (0.62); 1.3026 (0.49); 1.2470(0.69); 0.9883 (11.00); 0.9733 (11.80); 0.8749 (0.35); 0.8584 (1.02);0.8406 (0.46); 0.6207 (3.68); 0.6086 (3.79); 0.5475 (0.41); 0.5358(0.34); 0.4909 (4.55); 0.4834 (4.72); −0.0002 (4.84) I.47 DMSO- 4007.1766 (2.41); 7.1550 (3.37); 7.1394 (2.84); 7.0823 (2.56); 7.0759(2.99); 7.0611 d6 (4.50); 7.0545 (5.58); 7.0411 (3.62); 7.0339 (2.89);6.9867 (2.72); 6.9641 (2.91); 6.9120 (1.55); 5.7604 (14.89); 5.5311(2.98); 4.6505 (4.66); 3.9045 (14.38); 3.3139 (41.72); 2.7481 (0.95);2.7381 (2.08); 2.7299 (2.84); 2.7205 (4.06); 2.7110 (2.88); 2.7038(2.41); 2.6936 (1.32); 2.6860 (0.69); 2.6814 (0.94); 2.6769 (1.15);2.6724 (0.89); 2.5303 (2.69); 2.5255 (4.66); 2.5169 (55.06); 2.5124(114.36); 2.5079 (157.87); 2.5033 (115.77); 2.4989 (58.91); 2.3393(1.53); 2.3348 (1.88); 2.3301 (1.66); 2.3258 (1.37); 2.2708 (2.50);2.2286 (2.23); 2.1912 (2.36); 2.1468 (1.39); 1.7662 (5.40); 1.3946(1.56); 1.0153 (15.36); 1.0008 (16.00); 0.5065 (4.53); 0.4456 (5.32)I.48 CDCl3 400 7.2597 (23.44); 7.1067 (1.81); 7.0920 (2.09); 7.0855(3.36); 7.0709 (2.32); 7.0562 (1.28); 7.0524 (1.17); 7.0357 (0.38);7.0297 (0.47); 7.0122 (1.56); 7.0104 (1.48); 6.9412 (1.12); 6.9344(1.02); 6.9203 (2.05); 6.9137 (1.75); 6.8991 (1.26); 6.8928 (1.15);6.8840 (0.40); 6.8740 (3.06); 6.7375 (1.52); 6.7357 (1.51); 6.6548(0.41); 6.6460 (0.35); 5.6631 (1.25); 5.6248 (1.44); 5.6010 (1.25);5.5739 (1.55); 5.5630 (2.57); 5.3448 (0.34); 5.2977 (2.76); 5.1894(1.55); 5.1512 (1.30); 5.1206 (1.53); 5.0824 (1.35); 4.7897 (0.33);4.7648 (0.33); 4.5873 (0.34); 4.5553 (0.36); 3.8949 (16.00); 3.8036(3.75); 2.9535 (0.60); 2.9509 (0.66); 2.9432 (0.90); 2.9355 (1.23);2.9329 (1.23); 2.9249 (0.92); 2.9173 (0.66); 2.9147 (0.63); 2.3413(0.35); 2.3320 (0.38); 2.3063 (0.94); 2.3013 (0.92); 2.2972 (0.95);2.2858 (0.69); 2.2589 (1.20); 2.2530 (1.09); 2.2414 (0.80); 2.2207(0.63); 2.2158 (0.65); 1.8636 (0.84); 1.8602 (0.84); 1.8560 (0.88);1.8498 (0.79); 1.8400 (1.08); 1.8315 (1.50); 1.8250 (1.41); 1.8172(1.21); 1.8090 (1.07); 1.7951 (1.55); 1.7793 (0.99); 1.7702 (0.82);1.7540 (0.43); 1.7456 (0.38); 1.7375 (0.41); 1.5376 (8.67); 1.4389(0.39); 1.4316 (0.52); 1.4248 (0.55); 1.4179 (0.57); 1.4125 (0.50);1.4070 (0.50); 1.3992 (0.55); 1.3920 (0.47); 1.3858 (0.43); 1.0493(7.43); 1.0338 (7.91); 1.0258 (2.19); 1.0101 (1.82); 0.8261 (0.42);0.8233 (0.49); 0.8152 (0.48); 0.7059 (0.89); 0.7026 (1.37); 0.6920(2.33); 0.6840 (2.46); 0.6774 (1.48); 0.6739 (1.80); 0.6676 (0.93);0.5824 (0.74); 0.5783 (1.17); 0.5710 (2.73); 0.5646 (2.00); 0.5528(2.72); 0.5471 (1.45); 0.5371 (0.48); 0.0080 (0.59); −0.0002 (16.68);−0.0085 (0.54) I.49 CDCl3 300 7.6326 (0.87); 7.6079 (0.92); 7.3121(1.09); 7.2842 (0.39); 7.2770 (0.42); 7.2620 (50.60); 7.2367 (0.63);7.2170 (4.68); 7.2045 (6.01); 7.1974 (7.70); 7.1866 (16.50); 7.1766(10.62); 7.1674 (3.13); 7.1636 (2.81); 7.1594 (2.64); 7.1448 (1.74);7.1268 (3.16); 7.1165 (5.87); 7.1063 (3.43); 7.1020 (3.78); 7.0983(4.27); 7.0875 (2.92); 7.0852 (2.85); 7.0769 (0.62); 6.9460 (0.98);6.9110 (0.35); 5.7554 (1.81); 5.7342 (3.58); 5.7125 (1.92); 5.3001(16.00); 4.7289 (5.97); 3.9505 (13.76); 2.6330 (1.73); 2.4400 (3.70);2.4257 (3.93); 2.4103 (4.17); 2.2569 (3.07); 2.2357 (5.18); 2.2199(5.80); 2.1987 (3.77); 2.0458 (1.45); 1.8609 (0.97); 1.8422 (2.68);1.8229 (5.60); 1.8045 (4.90); 1.7945 (2.50); 1.7845 (2.58); 1.6735(2.34); 1.6650 (2.08); 1.6543 (4.30); 1.6469 (3.34); 1.6371 (5.71);1.6281 (5.46); 1.6193 (5.37); 1.6089 (6.26); 1.6008 (5.13); 1.5908(7.18); 1.5795 (20.35); 1.5534 (2.20); 1.2836 (0.71); 1.2597 (1.82);1.2413 (0.45); 1.2359 (0.58); 0.9036 (0.39); 0.8819 (1.21); 0.8585(0.46); 0.6424 (10.13); 0.6344 (10.03); 0.0107 (0.85); −0.0002 (31.52);−0.0111 (1.43) I.50 CDCl3 300 7.3634 (1.52); 7.2607 (25.70); 7.2500(0.48); 7.2485 (0.44); 7.2456 (0.34); 7.1902 (11.54); 7.1811 (9.18);7.1764 (6.33); 7.1608 (1.21); 7.1426 (0.41); 7.1227 (0.34); 7.1130(0.86); 7.1067 (2.19); 7.1002 (1.75); 7.0943 (1.76); 7.0886 (1.27);7.0841 (1.76); 7.0750 (1.21); 7.0669 (0.39); 6.9823 (1.63); 6.9152(1.34); 6.8786 (2.94); 6.8728 (2.60); 5.7632 (1.37); 5.7417 (2.99);5.7202 (1.46); 5.2996 (1.56); 4.7466 (11.02); 3.6625 (16.00); 2.6858(0.39); 2.6673 (1.02); 2.6496 (1.53); 2.6313 (1.01); 2.6128 (0.46);2.4524 (2.45); 2.4345 (2.10); 2.4170 (2.77); 2.3066 (0.52); 2.2662(1.40); 2.2451 (2.31); 2.2293 (2.52); 2.2079 (1.62); 1.8609 (0.47);1.8415 (1.22); 1.8226 (2.49); 1.8042 (2.15); 1.7942 (1.07); 1.7845(1.11); 1.6775 (1.16); 1.6696 (0.98); 1.6581 (2.03); 1.6500 (1.53);1.6409 (2.74); 1.6313 (2.43); 1.6230 (2.43); 1.6125 (2.71); 1.6042(2.20); 1.5943 (2.78); 1.5835 (1.62); 1.5687 (21.79); 1.5580 (1.07);1.5565 (1.07); 1.2552 (0.34); 0.6477 (6.04); 0.6311 (13.72); 0.0106(0.54); −0.0002 (16.86); −0.0111 (0.69) I.51 CDCl3 300 7.3047 (2.48);7.2617 (31.68); 7.2463 (1.82); 7.2393 (2.24); 7.2220 (5.80); 7.2149(8.98); 7.2031 (6.29); 7.1913 (8.78); 7.1678 (1.86); 7.1600 (1.45);7.1129 (2.81); 6.9554 (1.06); 6.7727 (2.05); 6.5899 (1.06); 5.7612(2.28); 5.7436 (1.50); 5.2989 (16.00); 4.7895 (3.11); 4.4932 (0.54);3.9029 (13.32); 2.7126 (2.17); 2.4519 (3.71); 2.3661 (0.43); 2.3066(3.16); 2.2864 (5.07); 2.2732 (5.52); 2.2528 (3.51); 1.8434 (5.29);1.8259 (4.92); 1.8056 (2.60); 1.6567 (5.44); 1.6381 (6.32); 1.6208(6.34); 1.5896 (26.65); 1.2592 (0.75); 0.8818 (0.43); 0.8585 (0.33);0.7911 (0.51); 0.7537 (0.46); 0.6960 (0.63); 0.6741 (0.60); 0.5195(5.26); 0.4800 (4.13); 0.0106 (0.68); −0.0002 (20.51); −0.0111 (0.86)I.52 CDCl3 300 7.4229 (2.02); 7.4085 (1.95); 7.2912 (0.34); 7.2809(0.34); 7.2608 (13.18); 7.2477 (1.03); 7.2288 (2.66); 7.2227 (3.66);7.2116 (3.15); 7.1992 (3.34); 7.1756 (0.87); 7.1229 (1.16); 6.9414(1.16); 6.9247 (1.18); 5.7814 (1.09); 5.7623 (0.74); 5.2982 (16.00);4.8011 (3.61); 4.4174 (0.43); 2.5469 (0.91); 2.4704 (1.79); 2.2659(2.55); 1.8367 (2.43); 1.8204 (2.34); 1.6468 (2.61); 1.6287 (3.15);1.6117 (3.29); 1.5888 (11.87); 1.2557 (0.36); 0.8230 (0.55); 0.4456(2.77); 0.4355 (2.70); −0.0002 (8.28); −0.0112 (0.35) I.53 DMSO- 5007.2325 (0.73); 7.2192 (5.12); 7.2120 (7.72); 7.2049 (7.09); 7.1918(1.34); 7.1580 d6 (3.48); 7.1512 (3.17); 7.1404 (2.36); 7.0804 (5.95);7.0717 (2.94); 7.0635 (3.04); 6.9720 (5.52); 6.8642 (2.79); 5.7444(5.49); 5.6949 (1.50); 5.6828 (2.82); 5.6707 (1.60); 4.6169 (7.49);3.7939 (16.00); 3.2828 (30.58); 2.6213 (1.75); 2.4984 (13.77); 2.4954(10.58); 2.3981 (3.70); 2.3908 (3.73); 2.2402 (2.62); 2.2277 (4.65);2.2185 (4.97); 2.2060 (3.00); 1.8096 (1.01); 1.7979 (2.79); 1.7867(4.71); 1.7758 (3.95); 1.7636 (1.87); 1.6300 (3.40); 1.6203 (4.33);1.5871 (1.94); 1.5753 (3.65); 1.5650 (4.78); 1.5431 (1.52); 1.2372(0.34); 0.5992 (4.37); 0.5877 (4.58); 0.4828 (5.88); −0.0002 (4.29) I.54DMSO- 400 7.9598 (0.76); 7.3005 (3.38); 7.2950 (3.52); 7.2801 (4.15);7.2746 (4.38); 7.1485 d6 (5.64); 7.1439 (5.31); 7.1293 (3.29); 7.1197(7.93); 7.0993 (6.32); 6.9946 (6.37); 6.8598 (3.20); 5.7359 (1.54);5.7201 (3.03); 5.7045 (1.53); 4.6067 (9.14); 3.8119 (16.00); 3.3384(243.60); 2.8981 (5.68); 2.7386 (4.82); 2.6783 (1.84); 2.6740 (1.84);2.5316 (1.83); 2.5182 (34.02); 2.5139 (65.43); 2.5095 (84.08); 2.5050(61.13); 2.5008 (29.89); 2.4022 (3.43); 2.3916 (3.48); 2.3797 (3.61);2.3407 (0.53); 2.3363 (0.64); 2.3318 (0.49); 2.2506 (2.35); 2.2348(4.05); 2.2237 (4.25); 2.2080 (2.48); 1.7885 (3.98); 1.7755 (3.40);1.7603 (1.56); 1.6281 (3.16); 1.6158 (3.86); 1.5897 (2.76); 1.5752(3.36); 1.5626 (4.06); 1.2415 (0.40); 0.6416 (1.03); 0.6255 (4.27);0.6116 (4.32); 0.5530 (0.34); 0.4989 (5.01); 0.4925 (5.38); 0.4724(1.15) I.55 DMSO- 400 7.9527 (0.39); 7.4627 (2.06); 7.2656 (1.35);7.2598 (1.73); 7.2542 (1.67); 7.2394 d6 (1.95); 7.2338 (2.12); 7.1221(3.26); 7.1148 (2.71); 7.1108 (2.57); 7.0885 (4.20); 7.0742 (3.53);7.0684 (6.66); 6.9793 (1.32); 5.7320 (1.16); 5.7160 (2.62); 5.6999(1.19); 4.5972 (7.43); 3.6861 (16.00); 3.3231 (16.86); 2.8903 (2.87);2.8497 (0.60); 2.8421 (0.80); 2.8339 (1.04); 2.8252 (0.80); 2.7310(2.41); 2.5101 (15.93); 2.5060 (30.74); 2.5016 (39.79); 2.4971 (29.20);2.4929 (14.47); 2.3906 (2.04); 2.3778 (1.84); 2.3648 (2.20); 2.2257(1.12); 2.2102 (1.95); 2.1992 (2.01); 2.1833 (1.17); 1.7734 (1.91);1.7606 (1.62); 1.7449 (0.74); 1.6298 (0.84); 1.6168 (1.59); 1.6041(1.96); 1.5743 (1.17); 1.5585 (1.57); 1.5459 (1.94); 0.7271 (0.60);0.7094 (2.63); 0.6962 (2.68); 0.6922 (2.30); 0.6793 (0.75); 0.5308(0.87); 0.5196 (2.61); 0.5133 (2.81); 0.5047 (2.35); 0.4916 (0.64) I.56DMSO- 400 7.9527 (2.21); 7.2812 (3.65); 7.2608 (4.78); 7.2207 (4.61);7.1810 (1.63); 7.1187 d6 (3.92); 7.0987 (3.35); 7.0459 (2.91); 6.9115(1.38); 5.7348 (2.77); 5.7198 (1.69); 4.6256 (4.17); 4.4058 (0.35);3.9341 (0.75); 3.9040 (15.03); 3.3755 (0.40); 3.3348 (346.94); 3.2755(0.44); 3.2706 (0.39); 2.8910 (16.00); 2.7316 (14.33); 2.7083 (2.56);2.6815 (1.18); 2.6765 (1.13); 2.6719 (1.15); 2.6674 (0.87); 2.5113(40.50); 2.5071 (79.80); 2.5027 (104.47); 2.4982 (78.13); 2.4941(39.73); 2.4005 (4.22); 2.3339 (0.83); 2.3295 (1.01); 2.3253 (0.81);2.2546 (4.81); 1.7971 (4.85); 1.6257 (4.27); 1.5744 (5.19); 1.4100(0.35); 1.3928 (0.34); 1.2345 (1.11); 1.1950 (0.39); 1.1824 (1.06);1.1653 (0.41); 1.1588 (0.96); 1.0694 (2.54); 0.7574 (0.35); 0.7398(0.36); 0.5155 (4.28); 0.5012 (4.37); 0.4461 (5.05); −0.0002 (3.57) I.57DMSO- 400 8.3846 (1.53); 7.9528 (0.45); 7.3075 (1.30); 7.2783 (1.92);7.2728 (2.07); 7.2580 d6 (2.40); 7.2524 (2.58); 7.1716 (2.84); 7.1210(4.09); 7.1157 (3.87); 7.0978 (5.03); 7.0774 (4.11); 7.0356 (1.46);5.7344 (1.24); 5.7185 (2.62); 5.7025 (1.25); 4.6040 (8.59); 3.9928(0.60); 3.9287 (16.00); 3.9003 (0.40); 3.3381 (150.12); 2.8909 (3.20);2.8031 (1.08); 2.7312 (2.68); 2.5072 (35.94); 2.5028 (45.62); 2.4983(33.34); 2.3861 (2.47); 2.3740 (2.40); 2.3612 (2.67); 2.3340 (0.37);2.3296 (0.43); 2.1988 (1.45); 2.1833 (2.47); 2.1723 (2.63); 2.1567(1.61); 1.7644 (2.51); 1.7515 (2.19); 1.6109 (2.11); 1.5987 (2.59);1.5615 (1.24); 1.5468 (2.11); 1.5343 (2.59); 1.2344 (0.39); 1.1823(0.46); 1.0695 (0.68); 0.7169 (0.77); 0.6991 (3.21); 0.6859 (3.29);0.6692 (0.95); 0.5405 (1.18); 0.5293 (3.37); 0.5229 (3.62); 0.5148(2.88); 0.5016 (0.79); −0.0002 (0.94) I.58 DMSO- 400 7.9526 (2.13);7.7750 (1.89); 7.7687 (2.13); 7.7620 (2.10); 7.7555 (1.75); 7.3493 d6(2.65); 7.2830 (2.13); 7.2632 (2.74); 7.2020 (0.33); 7.1151 (2.06);7.0948 (1.96); 7.0837 (1.26); 7.0697 (2.22); 7.0568 (2.21); 6.9321(0.67); 6.9186 (0.63); 5.7582 (1.74); 4.6212 (5.46); 3.3339 (257.49);2.9842 (1.97); 2.8909 (16.00); 2.8240 (2.03); 2.7317 (13.67); 2.6763(1.83); 2.6716 (1.85); 2.5490 (0.38); 2.5113 (34.93); 2.5069 (67.03);2.5024 (85.94); 2.4979 (61.37); 2.4935 (29.05); 2.4115 (2.75); 2.3337(0.64); 2.3291 (0.74); 2.3247 (0.59); 2.2476 (3.11); 1.7948 (3.24);1.6260 (2.86); 1.5691 (3.80); 1.2344 (0.86); 1.1822 (1.71); 1.0692(2.03); 0.8077 (0.34); 0.6935 (0.35); 0.3809 (6.33); −0.0002 (6.29)

The following examples illustrate in a non-limiting manner thepreparation and efficacy of the compounds of formula (I) according tothe invention.

PREPARATION EXAMPLE 1 Preparation ofN-[2-(cyclopentenyl)-4-methylbenzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound 1.17)

In a 20 mL microwave vial are dissolved in 10 mL ofN,N-dimethylformamide, 200 mg (0.48 mmol) ofN-(2-bromo-4-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamideand 188 mg (0.96 mmol) of N,N-dicyclohexylmethylamine. The medium isdegassed with argon and 5.4 mg (0.024 mmol) of palladium (II) acetateare added followed by 14 mg (0.048 mmol) of tri-ter-butylphosphoniumtetrafluoroborate and 325 mg (4.8 mmol) of cyclopentene. The microwaveapparatus [Biotage Initiator™] is then heated at 160° C. for 20 minutes.The reaction mixture is cooled to ambient temperature, diluted by 50 mLof dichloromethane, filtered over a pad of silica gel, and successivelywashed by a 1N aqueous solution of HCl and a saturated aqueous solutionof LiCl. The organic phase is dried, concentrated and purified by columnchromatography on silica gel (gradient heptane/ethyl acetate) to yield100 mg (49% yield) ofN-[2-(cyclopentenyl)-4-methylbenzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamideas a 2:5:1 mixture of three isomers: (M+H)=404.

PREPARATION EXAMPLE 2 Preparation of5-chloro-N-[2-(cyclohex-1-en-1-yl)-5-fluorobenzyl]-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide(compound 1.44)

To a suspension of 300 mg (0.68 mmol) ofN-(2-bromo-5-fluorobenzyl)-5-chloro-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamidein a 10/1 mixture of toluene/water degassed with argon, are successivelyadded 190 mg (1.50 mmol) of cyclohex-1-en-ylboronic acid, 38 mg (0.137mmol) of tricyclohexylphosphine, 15 mg (0.069 mmol) of palladium (II)acetate and 437 mg (2.06 mmol) of tri-potassium phosphate. The mixtureis heated at 100° C. for 1 hour. The reaction mixture is cooled toambient temperature. 1 mL of water is added to the reaction mixture andthe organic phase is filtered over a cake of diatomaceous earth. Thecake is washed twice by dichloromethane and the combined organic phasesare concentrated under vacuum to give 516 mg of crude material. Apurification by column chromatography on silica gel (gradientheptane/ethyl acetate) yields 154 mg (49% yield) of5-chloro-N-[2-(cyclohex-1-en-1-yl)-5-fluorobenzyl]-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide:(M+H)=438.

PREPARATION EXAMPLE 3 Preparation ofN-{1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethyl}-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide(compound 1.25)

Step 1: preparation ofN-{1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethyl}cyclopropanamine(compound IIa.4)

To a solution of 510 mg (2.49 mmol) of1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethanone in 5 mL of methanolis added 0.5 g of 3 Å molecular sieves followed by addition of 285 mg (5mmol) of cyclopropylamine and 375 mg (6.24 mmol) of acetic acid. Thereaction mixture is stirred for 90 min at reflux. The reaction mixtureis then cooled to 0° C. and 235 mg (3.74 mmol) of sodiumcyanoborohydride are slowly added. The reaction mixture is furtherstirred for 2 hours at reflux. The cooled reaction mixture is filteredover a cake of diatomaceous earth and the cake is washed by ethylacetate. The aqueous phase is extracted by ethyl acetate and thecombined organic extracts are washed by a 1N aqueous solution of sodiumhydroxide followed by a saturated aqueous solution of NaCl and driedover a ChemElut™ cartridge. Vacuum concentration yields 810 mg of crudeN-{1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethyl}cyclopropanamine as abrown oil used as such in the next step: (M+H)=246.

Step 2: preparation ofN-{1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethyl}-N-cyclopropyl-3-(difluoro-methyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

To a solution of 810 mg (3.30 mmol) of crudeN-{1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethyl}cyclopropanamine in10 mL of tetrahydrofuran are successively added 772 mg (3.63 mmol) of5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbonyl chloride and 400 mg (3.96mmol) of triethylamine. The reaction mixture is heated at reflux for 2hours. The reaction mixture is diluted by water and filtered over aChemElut™ cartridge. Concentration and purification by columnchromatography on silica gel (gradient heptane/ethyl acetate) leaves 580mg of a beige oil which is further purified by preparative HPLC(gradient acetonitrile/water+0.1% HCO₂H) to yield 350 mg (25% yield) ofN-{1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethyl}-N-cyclopropyl-3-(difluoro-methyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamideas a colorless oil: (M+H)=422.

GENERAL PREPARATION EXAMPLE 4 Thionation of Amide of Formula (I) onChemspeed™ Apparatus

In a 13 mL Chemspeed™ vial is weighted 0.27 mmol of phosphorouspentasulfide (P₂5₅). 3 mL of a 0.18 M solution of the amide (I) (0.54mmol) in dioxane is added and the mixture is heated at reflux for twohours. The temperature is then cooled to 80° C. and 2.5 mL of water areadded. The mixture is heated at 80° C. for one more hour. 2 mL of waterare then added and the reaction mixture is extracted twice by 4 mL ofdichloromethane. The organic phase is deposited on a basic aluminacartridge (2 g) and eluted twice by 8 mL of dichloromethane. Thesolvents are removed and the crude thioamide derivative is analyzed byLCMS and NMR. Insufficiently pure compounds are further purified bypreparative LC.

EXAMPLE A In Vivo Preventive Test on Sphaerotheca fuliginea (PowderyMildew on Cucurbits)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO and then diluted with water to obtain thedesired active material concentration.

Gherkin plants (“Vert petit de Paris” variety), sown in starter cups ona 50/50 peat soil-pozzolana substrate and grown at 24° C., are treatedat the Z11 cotyledon stage by spraying with the active ingredientprepared as described above. Plants, used as controls, are treated withthe mixture of acetone/tween/DMSO/water not containing the activematerial.

After 24 hours, the plants are contaminated by spraying the cotyledonswith an aqueous suspension of Sphaerotheca fuliginea spores (100,000spores per mL). The spores are collected from infected plants. Thecontaminated gherkin plants are incubated at about 20° C. and at 70-80%relative humidity. Grading (% of efficacy) is carried out 12 days afterthe contamination, in comparison with the control plants.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table A:

TABLE A Example Efficacy I.1 100 I.2 94 I.3 100 I.7 100 I.19 100 I.25100 I.27 98 I.28 100 I.30 83 I.32 100 I.43 80 I.45 100 I.46 100 I.49 100I.50 100 I.51 83 I.53 100

EXAMPLE B In Vivo Preventive Test on Alternaria solani (Tomato)

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofN,N-dimethylacetamide Emulsifier: 1 part by weight ofalkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous spore suspension of Alternaria solani. The plants are thenplaced in an incubation cabinet at approximately 20° C. and a relativeatmospheric humidity of 100%.

The test is evaluated 3 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control while an efficacy of100% means that no disease is observed.

Under these conditions, high (at least 90%) protection is observed at adose of 100 ppm of active ingredient with the following compound fromtable B:

TABLE B Example Efficacy I.1 94

EXAMPLE C In Vivo Preventive Test on Alternaria brassicae (Leaf Spot onRadish)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Radish plants (“Pernod Clair” variety), sown in starter cups on a 50/50peat soil pozzolana substrate and grown at 17° C., are treated at thecotyledon stage by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the cotyledonswith an aqueous suspension of Alternaria brassicae spores (50,000 sporesper mL). The spores are collected from a 15-day-old culture. Thecontaminated radish plants are incubated at 20° C. and at 100% relativehumidity.

Grading (% of efficacy) is carried out 6 days after the contamination,in comparison with the control plants.

Under these conditions, high (at least 80%) to excellent (at least 90%)protection is observed at a dose of 500 ppm of active ingredient withthe following compounds from table C1:

TABLE C1 Example Efficacy I.1 98 I.7 80 I.19 96 I.32 98 I.45 98

Under the same conditions, excellent (at least 95%) protection isobserved at a dose of 500 and 100 ppm of active ingredient with compoundof example 1.32, whereas high (less than 80%) to average (less than 50%)protection is observed with the uncyclized analogue CMP1 claimed inpatent application WO-2010/130767 as in table C2:

TABLE C2 Example dose (ppm) Efficacy I.32 from this patent 500 98 100 98CMP1 from WO-2010/130767 500 80 100 50

CMP1 claimed in international patent WO-2010/130767 corresponds toN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-{1-[2-(prop-1-en-2-yl)phenyl]ethyl}-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have amuch better biological activity than the structurally closest compoundsdisclosed in WO-2010/130767.

EXAMPLE D In Vivo Preventive Test on Venturia inaequalis (Apples)

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofN,N-dimethylacetamide Emulsifier: 1 part by weight ofalkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous conidia suspension of the causal agent of apple scab (Venturiainaequalis) and then remain for 1 day in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and arelative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

Under these conditions, excellent (at least 95%) protection is observedat a dose of 100 ppm of active ingredient with the following compoundfrom table D:

TABLE D Example Efficacy I.1 98

EXAMPLE E In Vivo Preventive Test on Botrytis cinerea (Beans)

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofN,N-dimethylacetamide Emulsifier: 1 part by weight ofalkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound. After the spray coating has dried on, 2small pieces of agar covered with growth of Botrytis cinerea are placedon each leaf. The inoculated plants are placed in a darkened chamber at20° C. and a relative atmospheric humidity of 100%.

2 days after the inoculation, the size of the lesions on the leaves isevaluated. 0% means an efficacy which corresponds to that of theuntreated control, while an efficacy of 100% means that no disease isobserved.

Under these conditions, excellent (at least 95%) protection is observedat a dose of 100 ppm of active ingredient with the following compoundfrom table E1:

TABLE E1 Example Efficacy I.1 98

Under the same conditions, excellent (at least 95%) protection isobserved at a dose of 250 and 100 ppm of active ingredient with compoundof example 1.1, whereas poor (less than 20%) to no protection isobserved a dose of 500 and 100 ppm with the uncyclized analogues CMP2and CMP3 claimed in patent application WO-2007/087906 as in table E2:

TABLE E2 Example dose (ppm) Efficacy I.1 from this patent 250 98 100 98CMP2 from WO-2007/087906 500 18 100 0 CMP3 from WO-2007/087906 500 0 1000

CMP2 claimed in international patent WO-2007/087906 corresponds toN-[5-chloro-2-(prop-1-en-2-yl)benzyl]-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide,and CMP3 claimed in international patent WO-2007/087906 corresponds toN-[5-chloro-2-(3-methylbut-2-en-2-yl)benzyl]-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have amuch better biological activity than the structurally closest compoundsdisclosed in WO-2007/087906.

EXAMPLE F In Vivo Preventive Test on Botrytis cinerea (Grey Mould)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO and then diluted with water to obtain thedesired active material concentration.

Gherkin plants (“Vert petit de Paris” variety), sown in starter cups ona 50/50 peat soil pozzolana substrate and grown at 24° C., are treatedat the Z11 cotyledon stage by spraying with the active ingredientprepared as described above. Plants, used as controls, are treated withthe mixture of acetone/tween/DMSO/water not containing the activematerial.

After 24 hours, the plants are contaminated by spraying the cotyledonswith an aqueous suspension of cryopreserved Botrytis cinerea spores(50,000 spores per mL). The spores are suspended in a nutrient solutioncomposed of 10 g/L of PDB, 50 g/L of D-Fructose, 2 g/L of NH₄NO₃ and 1g/L of KH₂PO₄. The contaminated gherkin plants are incubated at 17° C.and at 90% relative humidity.

Grading (% of efficacy) is carried out 4 to 5 days after thecontamination, in comparison with the control plants.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table F:

TABLE F Example Efficacy I.2 100 I.4 77 I.18 100 I.25 100 I.27 100 I.28100 I.30 81 I.31 100 I.49 100 I.50 98 I.53 100

EXAMPLE G In Vivo Preventive Test on Leptosphaeria nodorum Test (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier:  1 partby weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are sprayed with aspore suspension of Leptosphaeria nodorum. The plants remain for 48hours in an incubation cabinet at approximately 20° C. and a relativeatmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature ofapproximately 22° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 7-9 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

Under these conditions, excellent (at least 95%) protection is observedat a dose of 100 ppm of active ingredient with the following compoundfrom table G:

TABLE G Example Efficacy I.1 95

EXAMPLE H In Vivo Preventive Test on Pyrenophora teres (Barley)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Barley plants (“Plaisant” variety), sown in starter cups on a 50/50 peatsoil pozzolana substrate and grown at 22° C., are treated at the 1 leafstage (10 cm height) by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Pyrenophora teres spores (12,000 spores permL). The spores are collected from a 12-day-old culture. Thecontaminated barley plants are incubated for 48 hours at 20° C. and at100% relative humidity, and then for 12 days at 20° C. at 70-80%relative humidity.

Grading (% of efficacy) is carried out 14 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table H1:

TABLE H1 Example Efficacy I.1 97 I.7 86 I.19 93 I.25 100 I.28 79 I.32 97I.43 71 I.45 97 I.49 79 I.53 79

Under the same conditions, good (at least 70%) to excellent (at least90%) protection is observed at a dose of 100 ppm of active ingredientwith the following compounds from table H2:

TABLE H2 Example Efficacy I.3 86 I.8 71 I.9 79 I.20 97 I.22 71 I.33 86I.34 79 I.57 79

EXAMPLE I In Vivo Preventive Test on Puccinia recondita (Brown Rust onWheat)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Wheat plants (“Scipion” variety), sown in starter cups on a 50/50 peatsoil pozzolana substrate and grown at 22° C., are treated at the 1 leafstage (10 cm height) by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Puccinia recondita spores (100,000 spores permL). The spores are collected from an infected plant and are suspendedin water containing 2.5 mL/L of Tween 80 at 10%. The contaminated wheatplants are incubated for 24 hours at 20° C. and at 100% relativehumidity, and then for 10 days at 20° C. and at 70-80% relativehumidity.

Grading (% of efficacy) is carried out 12 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table I:

TABLE I Example Efficacy I.1 81 I.2 94 I.3 98 I.4 100 I.7 81 I.19 98I.27 88 I.28 100 I.29 81 I.32 98 I.43 78 I.44 81 I.45 81 I.46 75 I.47 81I.49 81 I.50 81 I.51 88 I.53 98

EXAMPLE J In Vivo Preventive Test on Septoria tritici (Wheat)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Wheat plants (“Scipion” variety), sown in starter cups on a 50/50 peatsoil pozzolana substrate and grown at 22° C., are treated at the 1 leafstage (10 cm height) by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of cryopreserved Septoria tritici spores (500,000spores per mL). The contaminated wheat plants are incubated for 72 hoursat 18° C. and at 100% relative humidity, and then for 21 days at 90%relative humidity.

Grading (% of efficacy) is carried out 24 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table J:

TABLE J Example Efficacy I.1 97 I.2 88 I.3 98 I.7 97 I.19 97 I.25 100I.27 94 I.28 94 I.32 100 I.43 97 I.44 79 I.45 100 I.46 86 I.49 88 I.50100 I.51 81 I.53 100

EXAMPLE K In Vivo Preventive Test on Uromyces appendiculatus (Bean Rust)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Bean plants (“Saxa” variety), sown in starter cups on a 50/50 peat soilpozzolana substrate and grown at 24° C., are treated at the 2 leaf stage(9 cm height) by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Uromyces appendiculatus spores (150,000 sporesper mL). The spores are collected from infected plants and are suspendedin water containing 2.5 mL/L of Tween 80 at 10%. The contaminated beanplants are incubated for 24 hours at 20° C. and at 100% relativehumidity, and then for 10 days at 20° C. and at 70-80% relativehumidity.

Grading (% of efficacy) is carried out 11 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table K1:

TABLE K1 Example Efficacy I.2 100 I.3 100 I.4 99 I.6 88 I.7 98 I.19 100I.27 98 I.28 100 I.29 84 I.30 78 I.43 89 I.45 75 I.49 99 I.50 99 I.51 96I.52 75 I.53 100

Under the same conditions, high (at least 80%) to total protection isobserved at a dose of 500 ppm of active ingredient with compound ofexample 1.3 (respectively 1.27, 1.28 and 1.29) whereas poor (less than20%) protection or plant damages is observed with the saturated analogueCMP4 (respectively CMP5, CMP6 and CMP7) claimed in patent applicationsWO-2007/087906 or WO-2010/130767 as in table K2:

TABLE K2 Example dose (ppm) Efficacy I.3 from this invention 500 100 100 99 CMP4 from WO-2010/130767 500 —^((a)) 100 100  I.27 from thisinvention 500 98 100 24 CMP5 from WO-2007/087906 500 —^((b)) 100  0 I.28from this invention 500 100  100 98 CMP6 from WO-2010/130767 500 —^((c))100    38^((d)) I.29 from this invention 500 84 100 35 CMP7 fromWO-2010/130767 500 13 100  0 note ^((a))together with 50% of plantdamages note ^((b))together with 60% of plant damages note^((c))together with 80% of plant damages note ^((d))together with 40% ofplant damages

CMP4 claimed in international patent WO-2010/130767 corresponds toN-(2-cyclopentylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide,CMP5 claimed in international patent WO-2007/087906 corresponds toN-(2-cyclohexylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,CMP6 claimed in international patent WO-2010/130767 corresponds toN-(2-cyclohexylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide,and CMP7 claimed in international patent WO-2010/130767 corresponds to5-chloro-N-(2-cyclohexylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have amuch better biological activity than the structurally closest compoundsdisclosed in WO-2007/087906 or in WO-2010/130767.

1. A compound of formula (I)

wherein A represents a carbo-linked, unsaturated or partially saturated,5-membered heterocyclyl group that can be substituted by up to fourgroups R that can be the same or different; T represents O or S; nrepresents 0, 1, 2, 3 or 4; m represents 0, 1, 2, 3, 4 or 5; prepresents 1, 2, 3 or 4; Z¹ represents a non-substitutedC₃-C₇-cycloalkyl or a C₃-C₇-cycloalkyl substituted by up to 10 atoms orgroups that can be the same or different and that can be selected in thelist consisting of halogen atoms, cyano, C₁-C₈-alkyl,C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different, C₁-C₈-alkoxy, C₁-C₈-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different, C₁-C₈-alkoxycarbonyl,C₁-C₈-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that canbe the same or different, C₁-C₈-alkylaminocarbonyl anddi-C₁-C₈-alkylaminocarbonyl; Z² and Z³, which can be the same ordifferent, represent a hydrogen atom; substituted or non substitutedC₁-C₈-alkyl; substituted or non substituted C₂-C₈-alkenyl; substitutedor non substituted C₂-C₈-alkynyl; cyano; isonitrile; nitro; a halogenatom; substituted or non substituted C₁-C₈alkoxy; substituted or nonsubstituted C₂-C₈-alkenyloxy; substituted or non substitutedC₂-C₈-alkynyloxy; substituted or non substituted C₃-C₇-cycloalkyl;substituted or non substituted C₁-C₈-alkylsulfanyl; substituted or nonsubstituted C₁-C₈alkylsulfonyl; substituted or non substitutedC₁-C₈-alkylsulfinyl; amino; substituted or non substitutedC₁-C₈-alkylamino; substituted or non substituted di-C₁-C₈-alkylamino;substituted or non substituted C₁-C₈-alkoxycarbonyl; substituted or nonsubstituted C₁-C₈-alkylcarbamoyl; substituted or non substituteddi-C₁-C₈-alkylcarbamoyl; or substituted or non substitutedN—C₁-C₈-alkyl-C₁-C₈alkoxycarbamoyl; or Z² and Z³ together with thecarbon atom to which they are linked can form a substituted or nonsubstituted C₃-C₇ cycloalkyl; or Z³ and the substituent X vicinal to thepoint of attachment of the phenyl ring, together with the consecutivecarbon atoms to which they are linked, can form a substituted or nonsubstituted 5-, 6- or 7-membered, partly saturated, carbo- orhetero-cycle comprising up to 3 heteroatoms and Z² is herein-described;X independently represents a halogen atom; nitro; cyano; isonitrile;hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl; formyl; formyloxy;formylamino; substituted or non-substituted (hydroxyimino)-C₁-C₈-alkyl;substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈alkyl;substituted or non-substituted (C₂-C₈alkenyloxyimino)-C₁-C₈-alkyl;substituted or non-substituted (C₂-C₈-alkynyloxyimino)-C₁-C₈-alkyl;substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; carboxy;carbamoyl; N-hydroxycarbamoyl; carbamate; substituted or non-substitutedC₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms;substituted or non-substituted C₂-C₈-alkenyl; C₂-C₈-halogenoalkenylhaving 1 to 9 halogen atoms; substituted or non-substitutedC₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1 to 9 halogen atoms;substituted or non-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylsulfanyl; C₁-C₈halogenoalkylsulfanyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylsulfinyl;C₁-C₈-halogenoalkylsulfinyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having1 to 9 halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;substituted or non-substituted di-C₁-C₈-alkylamino; substituted ornon-substituted C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy having 1 to 9halogen atoms; substituted or non-substituted C₃-C₈-alkynyloxy;C₂-C₈-halogenoalkynyloxy having 1 to 9 halogen atoms; substituted ornon-substituted C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 9halogen atoms; substituted or non-substituted C₄-C₇-cycloalkenyl;C₄-C₇-halogenocycloalkenyl having 1 to 9 halogen atoms; substituted ornon-substituted (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl; substituted ornon-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkenyl; substituted ornon-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkynyl; substituted ornon-substituted tri(C₁-C₈)alkylsilyl; substituted or non-substitutedtri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted or non-substitutedC₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylcarbonyloxy;C₁-C₈-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms; substitutedor non-substituted C₁-C₈-alkylcarbonylamino;C₁-C₈-halogenoalkylcarbonylamino having 1 to 9 halogen atoms;substituted or non-substituted C₁-C₈-alkoxycarbonyl;C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkyloxycarbonyloxy;C₁-C₈-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms; substitutedor non-substituted C₁-C₈-alkylcarbamoyl; substituted or non-substituteddi-C₁-C₈-alkylcarbamoyl; substituted or non-substitutedC₁-C₈-alkylaminocarbonyloxy; substituted or non-substituteddi-C₁-C₈-alkylaminocarbonyloxy; substituted or non-substitutedN—(C₁-C₈-alkyl)hydroxy carbamoyl; substituted or non-substitutedC₁-C₈-alkoxycarbamoyl; substituted or non-substitutedN—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl that can be substituted byup to 6 groups Q which can be the same or different; aryl-C₁-C₈-alkylthat can be substituted by up to 6 groups Q which can be the same ordifferent; aryl-C₂-C₈-alkenyl that can be substituted by up to 6 groupsQ which can be the same or different; aryl-C₂-C₈-alkynyl that can besubstituted by up to 6 groups Q which can be the same or different;aryloxy that can be substituted by up to 6 groups Q which can be thesame or different; arylsulfanyl that can be substituted by up to 6groups Q which can be the same or different; arylamino that can besubstituted by up to 6 groups Q which can be the same or different;aryl-C₁-C₈-alkyloxy that can be substituted by up to 6 groups Q whichcan be the same or different; aryl-C₁-C₈-alkylsulfanyl that can besubstituted by up to 6 groups Q which can be the same or different;aryl-C₁-C₈-alkylamino that can be substituted by up to 6 groups Q whichcan be the same or different; pyridinyl which can be substituted by upto 4 groups Q; pyridinyloxy which can be substituted by up to 4 groupsQ; Y independently represents a halogen atom; cyano; hydroxy; amino;sulfanyl; substituted or non-substituted C₁-C₈-alkyl;C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylsulfanyl;C₁-C₈-halogenoalkylsulfanyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylamino; substituted ornon-substituted di-C₁-C₈-alkylamino; substituted or non-substitutedC₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkoxycarbonyl;C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms; aryl that canbe substituted by up to 6 groups Q which can be the same or different;or Two geminal Y together with the carbon atom to which they are linkedcan form a carbonyl group C(═O); Q independently represents a halogenatom, cyano, nitro, substituted or non-substituted C₁-C₈-alkyl,C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different, substituted or non-substituted C₁-C₈alkoxy,C₁-C₈halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different, substituted or non-substituted C₁-C₈alkylsulfanyl,C₁-C₈halogenoalkylsulfanyl comprising up to 9 halogen atoms that can bethe same or different, substituted or non-substitutedtri(C₁-C₈)alkylsilyl, substituted or non-substitutedtri(C₁-C₈)alkylsilyl-C₁-C₈alkyl, substituted or non-substituted(C₁-C₈-alkoxyimino)-C₁-C₈alkyl, or substituted or non-substituted(benzyloxyimino)-C₁-C₈alkyl; R independently represents hydrogen atom;halogen atom; nitro; cyano; hydroxy; amino; sulfanyl;pentafluoro-λ⁶-sulfanyl; substituted or non-substituted(C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or non-substituted(benzyloxyimino)-C₁-C₈-alkyl; substituted or non-substitutedC₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms;substituted or non-substituted C₂-C₈-alkenyl; C₂-C₈-halogenoalkenylhaving 1 to 9 halogen atoms; substituted or non-substitutedC₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1 to 9 halogen atoms;substituted or non-substituted C₁-C₈alkoxy; C₁-C₈-halogenoalkoxy having1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylsulfinyl;C₁-C₈-halogenoalkylsulfinyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having1 to 9 halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;substituted or non-substituted di-C₁-C₈-alkylamino; substituted ornon-substituted C₂-C₈-alkenyloxy; substituted or non-substitutedC₃-C₈-alkynyloxy; substituted or non-substituted C₃-C₇-cycloalkyl;C₃-C₇-halogenocycloalkyl having 1 to 9 halogen atoms; substituted ornon-substituted tri(C₁-C₈)alkylsilyl; substituted or non-substitutedC₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkoxycarbonyl;C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylcarbamoyl; substituted or non-substituteddi-C₁-C₈-alkylcarbamoyl; phenoxy; phenylsulfanyl; phenylamino;benzyloxy; benzylsulfanyl; or benzylamino; as well as its salts,N-oxides, metal complexes, metalloid complexes and optically activeisomers or geometric isomers thereof.
 2. A compound according to claim 1wherein A is selected in the list consisting of: a heterocycle offormula (A1)

wherein R¹ to R³ that can be the same or different represent a hydrogenatom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl;C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different; substituted or non-substituted C₁-C₅-alkoxy orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different; a heterocycle of formula (A2)

wherein: R⁴ to R⁶ that can be the same or different represent a hydrogenatom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl;C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different; substituted or non-substituted C₁-C₅-alkoxy orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different; a heterocycle of formula (A³)

wherein: R⁷ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; substituted ornon-substituted C₁-C₈-alkoxy or C₁-C₈-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different; R⁸ represents ahydrogen atom or a substituted or non-substituted C₁-C₅-alkyl; aheterocycle of formula (A⁴)

wherein: R⁹ to R¹¹ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; amino; substituted or non-substituted C₁-C₅-alkoxy;substituted or non-substituted C₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkylcomprising up to 9 halogen atoms that can be the same or different orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different; a heterocycle of formula (A⁵)

wherein: R¹² and R¹³ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy; amino;C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different or C₁-C₅-halogenoalkoxy comprising up to 9 halogenatoms that can be the same or different; R¹⁴ represents a hydrogen atom;a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substitutedor non-substituted C₁-C₅-alkoxy; amino; C₁-C₅-halogenoalkyl comprisingup to 9 halogen atoms that can be the same or different orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different; a heterocycle of formula (A⁶)

wherein: R¹⁵ represents a hydrogen atom; a halogen atom; a cyano;substituted or non-substituted C₁-C₅-alkyl; substituted ornon-substituted C₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different or C₁-C₅-halogenoalkylcomprising up to 9 halogen atoms that can be the same or different; R¹⁶and R¹⁸ that can be the same or different represent a hydrogen atom; ahalogen atom; substituted or non-substituted C₁-C₅-alkoxycarbonyl;substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkoxycomprising up to 9 halogen atoms that can be the same or different orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different; R¹⁷ represent a hydrogen atom or substituted ornon-substituted C₁-C₅-alkyl; a heterocycle of formula (A⁷)

wherein: R¹⁹ represents a hydrogen atom or a C₁-C₅-alkyl R²⁰ to R²² thatcan be the same or different represent a hydrogen atom; a halogen atom;substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkylcomprising up to 9 halogen atoms that can be the same or different; aheterocycle of formula (A⁸)

wherein: R²³ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; R²⁴ represents ahydrogen atom or substituted or non-substituted C₁-C₅-alkyl orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different; a heterocycle of formula (A⁹)

wherein: R²⁵ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; R²⁶ represents ahydrogen atom; substituted or non-substituted C₁-C₅-alkyl orC₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different; a heterocycle of formula (A¹⁰)

wherein: R²⁷ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; R²⁸ represents ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; C₁-C₅-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different; amino; substituted ornon-substituted C₁-C₅-alkylamino or substituted or non-substituteddi(C₁-C₅-alkyl)amino; a heterocycle of formula (A¹¹)

wherein: R²⁹ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms thatcan be the same or different or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; R³⁰ represents ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; C₁-C₅-halogenoalkoxy comprising up to 9halogen atoms that can be the same or different; amino; substituted ornon-substituted C₁-C₅-alkylamino or substituted or non-substituteddi(C₁-C₅-alkyl)amino; a heterocycle of formula (A¹²)

wherein: R³¹ represents a hydrogen atom or a substituted ornon-substituted C₁-C₅-alkyl R³² represents a hydrogen atom; a halogenatom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkylcomprising up to 9 halogen atoms that can be the same or different; R³³represents a hydrogen atom; a halogen atom; a nitro; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms thatcan be the same or different or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; a heterocycle offormula (A¹³)

wherein: R³⁴ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₃-C₅-cycloalkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atomsthat can be the same or different; substituted or non-substitutedC₁-C₅-alkoxy; substituted or non-substituted C₂-C₅-alkynyloxy orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different; R³⁵ represents a hydrogen atom; a halogen atom;substituted or non-substituted C₁-C₅-alkyl; a cyano; substituted ornon-substituted C₁-C₅-alkoxy; substituted or non-substitutedC₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkyl comprising up to 9 halogenatoms that can be the same or different; C₁-C₅-halogenoalkoxy comprisingup to 9 halogen atoms that can be the same or different; amino;substituted or non-substituted C₁-C₅-alkylamino or substituted ornon-substituted di(C₁-C₅-alkyl)amino; R³⁶ represents a hydrogen atom orsubstituted or non-substituted C₁-C₅-alkyl; a heterocycle of formula(A¹⁴)

wherein: R³⁷ and R³⁸ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; substituted or non-substitutedC₁-C₅-alkoxy or a substituted or non-substituted C₁-C₅-alkylsulfanyl;R³⁹ represents a hydrogen atom or substituted or non-substitutedC₁-C₅-alkyl; a heterocycle of formula (A¹⁵)

wherein: R⁴⁰ and R⁴¹ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; a heterocycle of formula (A¹⁶)

wherein: R⁴² and R⁴³ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different or amino; a heterocycle of formula (A¹⁷)

wherein: R⁴⁴ and R⁴⁵ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; a heterocycle of formula (A¹⁸)

wherein: R⁴⁷ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; R⁴⁶ represents ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different or substituted or non-substitutedC₁-C₅-alkyl sulfanyl; a heterocycle of formula (A¹⁹)

wherein: R⁴⁹ and R⁴⁸ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy;C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different or C₁-C₅-halogenoalkyl comprising up to 9 halogenatoms that can be the same or different; a heterocycle of formula (A²⁰)

wherein: R⁵⁰ and R⁵¹ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy;C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different or C₁-C₅-halogenoalkyl comprising up to 9 halogenatoms that can be the same or different; a heterocycle of formula (A²¹)

wherein: R⁵² represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different. a heterocycle offormula (A²²)

wherein: R⁵³ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different. a heterocycle offormula (A²³)

wherein: R⁵⁴ and R⁵⁶ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; R⁵⁵ represents a hydrogen atom orsubstituted or non-substituted C₁-C₅-alkyl; a heterocycle of formula(A²⁴)

wherein: R⁵⁷ and R⁵⁹ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; R⁵⁸ represents a hydrogen atom orsubstituted or non-substituted C₁-C₅-alkyl; a heterocycle of formula(A²⁵)

wherein: R⁶⁰ and R⁶¹ that can be the same or different represent ahydrogen atom; a halogen atom; substituted or non-substitutedC₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms thatcan be the same or different; R⁶² represents a hydrogen atom orsubstituted or non-substituted C₁-C₅-alkyl; a heterocycle of formula(A²⁶)

wherein: R⁶⁵ represents a hydrogen atom; a halogen atom; substituted ornon-substituted C₁-C₅-alkyl; substituted or non-substitutedC₃-C₅-cycloalkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atomsthat can be the same or different; substituted or non-substitutedC₁-C₅-alkoxy; substituted or non-substituted C₂-C₅-alkynyloxy orC₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different; R⁶³ represents a hydrogen atom; a halogen atom;substituted or non-substituted C₁-C₅-alkyl; a cyano; substituted ornon-substituted C₁-C₅-alkoxy; substituted or non-substitutedC₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkyl comprising up to 9 halogenatoms that can be the same or different; C₁-C₅-halogenoalkoxy comprisingup to 9 halogen atoms that can be the same or different; amino;substituted or non-substituted C₁-C₅-alkylamino or di(C₁-C₅-alkyl)amino;R⁶⁴ represents a hydrogen atom or substituted or non-substitutedC₁-C₅-alkyl.
 3. A compound according to claim 1 wherein A is selected inthe list consisting of A²; A⁵; A⁶; A¹⁰ and A¹³.
 4. A compound accordingto claim 3 wherein A represents A¹³ wherein R³⁴ represents a substitutedor non-substituted C₁-C₅-alkyl, C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different; substituted ornon-substituted C₁-C₅-alkoxy; R³⁵ represents a hydrogen atom or ahalogen atom and R³⁶ represents a substituted or non-substitutedC₁-C₅-alkyl.
 5. A compound according to claim 4 wherein A represents A¹³wherein R³⁴ represents C₁-C₅-alkyl, C₁-C₅-halogenoalkyl comprising up to3 halogen atoms that can be the same or different; R³⁵ represents ahydrogen atom; a chlorine atom; or a fluorine atom; and R³⁶ represents amethyl.
 6. A compound according to claim 1 wherein T represents O.
 7. Acompound according to claim 1 wherein Z¹ represents a substituted ornon-substituted cyclopropyl.
 8. A compound according to claim 7 whereinZ¹ represents a non-substituted cyclopropyl or a2-C₁-C₅-alkylcyclopropyl.
 9. A compound according to claim 1 wherein Z²and Z³ independently represent a hydrogen atom or a C₁-C₈-alkyl.
 10. Acompound according to claim 1 wherein X independently, represents ahalogen atom; substituted or non substituted C₁-C₈-alkyl;C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms which can be thesame or different; substituted or non substituted C₃-C₇-cycloalkyl;tri(C₁-C₈-alkyl)silyl; or substituted or non substituted C₁-C₈-alkylsulfanyl.
 11. A compound according to claim 1 wherein Y independently,represents a halogen atom; substituted or non substituted C₁-C₈-alkyl;C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms which can be thesame or different; substituted or non substituted C₁-C₈-alkoxy; orC₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms which can be thesame or different.
 12. A compound of formula (IIa)

wherein n represents 0, 1, 2, 3, or 4; m represents 0, 1, 2, 3, 4 or 5;p represents 1, 2, 3 or 4; Z² and Z³ which can be the same or differentrepresent a hydrogen atom; substituted or non substituted C₁-C₈-alkyl;substituted or non substituted C₇-C₈-alkenyl; substituted or nonsubstituted C₂-C₈-alkenyl; cyano; isonitrile; nitro; a halogen atom;substituted or non substituted C₁-C₈-alkoxy; substituted or nonsubstituted C₂-C₈-alkenyloxy; substituted or non substitutedC₇-C₈-alkynyloxy; substituted or non substituted C₃-C₇-cycloalkyl;substituted or non substituted C₁-C₈-alkylsulfanyl; substituted or nonsubstituted C₁-C₈-alkylsulfonyl; substituted or non substitutedC₁-C₈-alkylsulfinyl; amino; substituted or non substitutedC₁-C₈-alkylamino; substituted or non substituted di-C₁-C₈-alkylamino;substituted or non substituted C₁-C₈-alkoxycarbonyl; substituted or nonsubstituted C₁-C₈-alkylcarbamoyl; substituted or non substituteddi-C₁-C₈-alkylcarbamoyl; or substituted or non substitutedN—C₁-C₈-alkyl-C₁-C₈alkoxy-carbamoyl; or Z² and Z³ together with thecarbon atom to which they are linked can form a substituted or nonsubstituted C₃-C₇ cycloalkyl; or Z³ and the substituent X vicinal to thepoint of attachment of the phenyl ring, together with the consecutivecarbon atoms to which they are linked, can form a substituted or nonsubstituted 5-, 6- or 7-membered, partly saturated, carbo- orhetero-cycle comprising up to 3 heteroatoms and Z² is herein-described;X independently represents a halogen atom; nitro; cyano; isonitrile;hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl; formyl; formyloxy;formylamino; substituted or non-substituted (hydroxyimino)-C₁-C₈-alkyl;substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;substituted or non-substituted (C₂-C₈-alkenyloxyimino)-C₁-C₈-alkyl;substituted or non-substituted (C₂-C₈-alkynyloxyimino)-C₁-C₈-alkyl;substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; carboxy;carbamoyl; N-hydroxycarbamoyl; carbamate; substituted or non-substitutedC₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms;substituted or non-substituted C₂-C₈-alkenyl; C₂-C₈-halogenoalkenylhaving 1 to 9 halogen atoms; substituted or non-substitutedC₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1 to 9 halogen atoms;substituted or non-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylsulfinyl;C₁-C₈-halogenoalkylsulfinyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having1 to 9 halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;substituted or non-substituted di-C₁-C₈-alkylamino; substituted ornon-substituted C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy having 1 to 9halogen atoms; substituted or non-substituted C₃-C₈-alkynyloxy;C₂-C₈-halogenoalkynyloxy having 1 to 9 halogen atoms; substituted ornon-substituted C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 9halogen atoms; substituted or non-substituted C₄-C₇-cycloalkenyl;C₄-C₇-halogenocycloalkenyl having 1 to 9 halogen atoms; substituted ornon-substituted (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl; substituted ornon-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkenyl; substituted ornon-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkynyl; substituted ornon-substituted tri(C₁-C₈)alkylsilyl; substituted or non-substitutedtri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted or non-substitutedC₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylcarbonyloxy;C₁-C₈-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms; substitutedor non-substituted C₁-C₈-alkylcarbonylamino;C₁-C₈-halogenoalkylcarbonylamino having 1 to 9 halogen atoms;substituted or non-substituted C₁-C₈-alkoxycarbonyl;C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkyloxycarbonyloxy;C₁-C₈-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms; substitutedor non-substituted C₁-C₈-alkylcarbamoyl; substituted or non-substituteddi-C₁-C₈-alkylcarbamoyl; substituted or non-substitutedC₁-C₈-alkylaminocarbonyloxy; substituted or non-substituteddi-C₁-C₈-alkylaminocarbonyloxy; substituted or non-substitutedN—(C₁-C₈-alkyl)hydroxy carbamoyl; substituted or non-substitutedC₁-C₈-alkoxycarbamoyl; substituted or non-substitutedN—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl that can be substituted byup to 6 groups Q which can be the same or different; aryl-C₁-C₈-alkylthat can be substituted by up to 6 groups Q which can be the same ordifferent; aryl-C₂-C₈-alkenyl that can be substituted by up to 6 groupsQ which can be the same or different; aryl-C₂-C₈-alkynyl that can besubstituted by up to 6 groups Q which can be the same or different;aryloxy that can be substituted by up to 6 groups Q which can be thesame or different; arylsulfanyl that can be substituted by up to 6groups Q which can be the same or different; arylamino that can besubstituted by up to 6 groups Q which can be the same or different;aryl-C₁-C₈-alkyloxy that can be substituted by up to 6 groups Q whichcan be the same or different; aryl-C₁-C₈-alkylsulfanyl that can besubstituted by up to 6 groups Q which can be the same or different;aryl-C₁-C₈-alkylamino that can be substituted by up to 6 groups Q whichcan be the same or different; pyridinyl which can be substituted by upto 4 groups Q; pyridinyloxy which can be substituted by up to 4 groupsQ; Y independently represents a halogen atom; cyano; hydroxy; amino;sulfanyl; substituted or non-substituted C₁-C₈-alkyl;C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylsulfanyl;C₁-C₈-halogenoalkylsulfanyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylamino; substituted ornon-substituted di-C₁-C₈-alkylamino; substituted or non-substitutedC₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkoxycarbonyl;C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms; aryl that canbe substituted by up to 6 groups Q which can be the same or different;or Two geminal Y together with the carbon atom to which they are linkedcan form a carbonyl group C(═O) and; Q independently represents ahalogen atom, cyano, nitro, substituted or non-substituted C₁-C₈-alkyl,C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different, substituted or non-substituted C₁-C₈-alkoxy,C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms that can be thesame or different, substituted or non-substituted C₁-C₈-alkylsulfanyl,C₁-C₈-halogenoalkylsulfanyl comprising up to 9 halogen atoms that can bethe same or different, substituted or non-substitutedtri(C₁-C₈)alkylsilyl, substituted or non-substitutedtri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl, substituted or non-substituted(C₁-C₈-alkoxyimino)-C₁-C₈-alkyl, or substituted or non-substituted(benzyloxyimino)-C₁-C₈-alkyl as well as salts thereof.
 13. A compoundaccording to claim 12 selected from the list consisting of:N-{1-[2-(cyclopent-1-en-1-yl)phenyl]ethyl}cyclopropanamineN-[2-(cyclopent-1-en-1-yl)benzyl]cyclopropanamineN-[5-chloro-2-(cyclopent-1-en-1-yl)benzyl]cyclopropanamineN-{1-[2-(cyclopent-1-en-1-yl)-5-fluorophenyl]ethyl}cyclopropanamineN-[2-chloro-5-(cyclopent-1-en-1-yl)benzyl]cyclopropanamineN-[2-(cyclohex-1-en-1-yl)benzyl]cyclopropanamineN-[5-chloro-2-(cyclohex-1-en-1-yl)benzyl]cyclopropanamineN-[2-chloro-5-(cyclohex-1-en-1-yl)benzyl]cyclopropanamineN-[2-(cyclohept-1-en-1-yl)benzyl]cyclopropanamineN-[5-chloro-2-(cyclohept-1-en-1-yl)benzyl]cyclopropanamine.
 14. Afungicide composition comprising, as an active ingredient, an effectiveamount of a compound of formula (I) according to claim 1 and anagriculturally acceptable support, carrier or filler.
 15. A method forcontrolling phytopathogenic fungi of crops, characterized in that anagronomically effective and substantially non-phytotoxic quantity of acompound according to claim 1 is applied to the soil where plants growor are capable of growing, to the leaves and/or the fruit of plants orto the seeds of plants.
 16. Use of compounds of the formula (I)according to claim 1 for the control of phytopathogenic harmful fungi.17. Process for producing compositions for controlling phytopathogenicharmful fungi, characterized in that derivatives of the formula (I)according to claim 1 are mixed with extenders and/or surfactants. 18.Use of compounds of the formula (I) according to claim 1 for treatmentof plants, seeds, transgenic plants or transgenic seeds.
 19. A methodfor controlling phytopathogenic fungi of crops, characterized in that anagronomically effective and substantially non-phytotoxic quantity of acomposition according to claim 14 is applied to the soil where plantsgrow or are capable of growing, to the leaves and/or the fruit of plantsor to the seeds of plants.